De Ocampo started playing organized basketball at the Saint Francis of Assisi College System Doves together with his brother, Yancy. The De Ocampo brothers led the varsity squad to several NCRAA titles. Upon the exit of the older De Ocampo, the Doves was still dominating the league with him alongside Ervin Sotto and Al Vergara. Thus, he led the squad into several statistical categories such as scoring and rebounding. He won four NCRAA MVP plums making him arguably the finest player in the history of the NCRAA.
Professional career
In 2004, after a celebrated collegiate career at St. Francis, De Ocampo decided to turn pro and enter the PBA draft. He was selected by the FedEx Express as the fourth overall pick, having selected ahead of higher profile players such as classy UE point guard Paul Artadi, multi-titled PBL veteran Gary David and former Ateneo Blue Eagles star Wesley Gonzales. During his rookie year, he played alongside his brother Yancy. He played in a total of 59 games and averaged decent rookie numbers of 7.5 points and 4.6 rebounds while playing a little over 21 minutes of action per game. After a so-so performance in his first year, he made an impact in the 2005–06 season by improving his rookie numbers of 7.5 points per game to 13.3 in his sophomore year in 37 of 51 games played. He also registered 6.7 rebounds and 2.4 assists in that year. In 2008, de Ocampo was again included in the RP Training Pool, his second stint, assembled by the PBA under Coach Yeng Guiao. In the middle of the 2008–09 PBA Philippine Cup, he was traded to the Talk 'N Text Tropang Texters for veteran Don Allado. His all-around play helped them beat the Alaska Aces in that conference's finals series, 4-3, earning him his first PBA title.
In 2015, de Ocampo led the Texters to the 2015 PBA Commissioner's Cup championship, winning a seven-game series against Rain or Shine Elasto Painters. On April 29, 2015, de Ocampo was named as the Finals MVP. During the series, he averaged 24.3 points and 6.6 rebounds and as well as shooting at an impressive 40% from the three-point area over the course of seven games. On September 11, 2017, de Ocampo was dealt to the Meralco Bolts along with KaTropa's 2019 second round pick for Justin Chua and Norbert Torres in a three-team trade with Phoenix and Meralco. On April 13, 2020, de Ocampo announced his retirement from professional basketball.