Based on the traditional solar photovoltaic/thermal (PV/T) system, the experimental platform of compound parabolic collector (CPC) coupled PV/T system was constructed, and the measurement and control system (MCS) of the experimental platform was also proposed. According to the evaluation system of photothermal PV energy conversion performance, the change rule of photothermal power (PTP) of CPC coupled PV/T system was studied and analyzed when the inlet water temperature was 20°C and the ambient temperature was 28°C, as well as the change rule of thermal efficiency and photoelectric efficiency (PEE). When the solar radiation intensity reached 800 W/m2, the outlet water temperature of the system could reach more than 45°C under the condition that the power efficiency of the system was more than 10%, which could meet the demand of water and heating. The total amount of solar radiation in the whole day was 17.32 MJ/m2, the photoelectric output of CPC coupled PV/T system was 18.32 MJ, the average PEE was 9.2%, the collector heat was 99.33 MJ, the average photothermal efficiency was 50.1%, and the total efficiency of the system was 58.7%. In a word, compared with the traditional collector, the PV/T system proposed has better performance.