The natural convective heat transfer phenomenon in an isolated, walled CCPC with PV cell is studied experimentally at 1000 W/m² irradiance and 28.5 °C ambient temperature as well as 0°, 10°, 20°, 30° and 40° incidences in indoor laboratory by using solar simulator. Then a series of numerical simulations are launched to estimate the CCPC natural heat transfer behaviour and optical performance based on steady heat transfer and laminar flow models with grey optical option. It is identified that the heat transfer and optical performances of CCPC are dependent on the incidence. Especially, the PV cell is subject to the highest temperature at an incidence less than 20°, and otherwise the top glass cover is with the highest temperature. The predicted temperatures, Nusselt numbers and heat loss ratios are consistent with the experimental observations basically, especially at the incidence less than 20° with (−10.1~+3) % error in temperature, (−35.6~+12.6) % in Nusselt number, and (−1.2~+20.5) % in CCPC wall heat loss ratio. The optical parameters predicted agree very well with the measurements. The heat loss from the CCPC walls accounts for nearly 60% of the total incoming solar irradiance and should be paid significant attention in the design of CCPC.