The Board of Regents of the University of the Philippines formally approved the establishment of the College of Law on 21 January 1911. The College however, traces its beginnings to the law courses opened in 1910 by the Educational Department Committee of the Young Men's Christian Association (YMCA), through the effort of George A. Malcolm who was later to become the first permanent dean of the College.

In June 1911, the College was formally opened with first and second year classes. There was a total of 125 students comprising freshmen and sophomores, the latter numbering fifty when they started the YMCA school. Of this first law class one became a President of the Philippines, another, a Chief Justice of the Supreme Court, while several others became legislation and legal luminaries.

The faculty was at first predominantly American but the faculty profile changed when the American teachers were supplanted by Filipinos. Sherman Moreland, Justice of the Philippine Supreme Court, was acting Dean from July 1 to October 11, 1911; George Malcolm was Secretary and subsequently Dean until 1917 when he was elevated to the Supreme Court. Jorge C. Bocobo, a member of the 1911 faculty, succeeded Dean Malcolm and became the first Filipino dean of the College. He held that position until 1934.

In the early years of the College, classes were held after five o'clock in the afternoon because most of the students held some employment during the day. The College offered a three-year course for students devoting full time to their studies int the College and four-year course for students who were employed. Commencing with the school year 1917-1918, the four-year course was prescribed for all students.

By its twenty-fifth year, the enrollment in the College of Law totalled 547 students and the faculty was composed of eight full-time and nine part-time members. A graduate program leading to the Master of Laws degree had been established; two earned the degree in 1918. Classes were then held in Palma Hall on the Padre Faura Campus Manila and the greater number of students attended day classes. Evening classes were maintained for students who were employed during the day.

Dean Jose A. Espiritu was appointed in 1934 to succeed Dean Bocobo. Upon the outbreak of the war in 1941, the College was closed and classes did not resume until August of 1945. Returning from a brief stint in the Supreme Court, Dean Espiritu commenced the difficult task of rehabilitating the College.

In December 1948, with the transfer of the main campus of the University of the Philippines to Diliman, Quezon City, the College was assigned first an army hut, and later, a three-storey building named Malcolm Hall after the founder and first permanent dean.

Dean Espiritu retired in 1953 and was succeeded by Dean Vicente G. Sinco. Dean Sinco was appointed President of the University in 1958 and Judge Vicente Abad Santos, a former member of the law faculty, became dean. Dean Abad Santos held the deanship until 1969. Prof. Perfecto V. Fernandez was appointed Officer-in-Charge of the College about a year until Dr. Irene R. Cortes was appointed in 1970. Thus, she became the first woman to hold the position. In April 1978, Dr. Froilan M. Bacungan, then the Director of the Law Center, succeeded to the deanship. In October 1983, Prof. Bartolome S. Carale was appointed Dean of the College and served until April 1989. The College of Law and the Law Complex subsequently underwent a process of reorganization, and a new dean was not appointed until after its completion. Dr. Pacifico A. Agabin was appointed dean in October 1989 and served until October 1995 when Prof. Merlin M. Magallona became the tenth dean of the College. In August 1999, Dr. Raul C. Pangalangan was appointed dean of the College until his second term ended in September 2005. Prof. Salvador T. Carlota was the twelfth Dean of the College from October 2005 to April 2008. Prof. Marvic M.V.F. Leonen served as Dean from 2008 to 2011. Prof. Danilo Concepcion was elected Dean of the College in June 2011, and was elected President of the University in February 2017. Fides Cordero-Tan was elected Dean on February 2018.

A century after it was founded, the College of Law can point to its alumni in the highest positions of the government. Four held the post in each ones turn, of President: Jose P. Laurel Sr., Manuel A. Roxas, Elpidio R. Quirino, and Ferdinand E. Marcos. Thirteen served as Chief Justices of the Supreme Court; Ricardo M. Paras, Jose Y. Yulo, Cesar C. Bengzon, Querube C. Makalintal, Fred Ruiz Castro, Enrique M. Fernando, Felix V. Makasiar, Ramon C. Aquino, Pedro L. Yap, Marcelo B. Fernan, Hilario G. Davide, Jr. , Reynato S. Puno and the incumbent, Ma. Lourdes Aranal-Sereno . A sizeable percentage of the former and incumbent senators and members of the House of Representatives are also graduates of the College. Two College of Law alumni became Presidents of the University of the Philippines: Vicente G. Sinco and Edgardo J. Angara. Many more of its graduates are prominent law practitioners, high officials in government service, political leaders, as well as pioneers in private enterprises.