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He earned his political science and law degrees and three graduate degrees – Master of Public Administration, Master of Laws and Doctor of Laws at the University of Philippines, Diliman.
In his first term as a lawmaker, Senator Cayetano has filed a number of Senate bills and resolutions aimed at speeding up the dispensation of justice for criminal cases and in curbing graft and corruption. Through his efforts, the Supreme Court issued Administrative Order 51-96 designating special criminal courts in Metro Manila and other cities to hear cases involving heinous crimes and finish the trial within 60 days. A strong exponent of the rights of the consuming public, he filed Resolution No. 579 and fought for the ban on collection of parking fees by shopping malls. The Senate Committee on Commerce and Industry jointly with the Justice and Human Rights Committee found the collection of parking fees, and the provisions of the waiver of liability, stated in parking tickets are illegal.
He authored and co-authored landmark pieces of legislation during the 11th Congress which includes:
During the impeachment trial of former President Estrada, he was one of the ten Senator-Judges who voted for the opening of the second envelope, an event that triggered People Power II, which eventually led to the ousting of the former president.