Recently, there has been increasing attention on the use of renewable energy in buildings, particularly, the photovoltaic thermal (PVT) system that uses both solar power and thermal energy. However, there is a limit to adopting the PVT system in real buildings because many architects value the aesthetics of buildings or spaces. This study developed a curtain-wall-type liquid-type PVT (CW-PVT) that can be installed on a wall as it integrates with the building. To analyze the system performance, a real-scale experimental plant was established in an outdoor environment. The performance of the CW-PVT unit was verified for two different module pipe connection types: parallel and serial. Meteorological variable data, the inlet and outlet fluid temperatures, surface temperature, and electrical energy generation of the modules were measured and collected using the measurement equipment according to the module pipe connection type. Consequently, the parallel-type method was approximately 10% more efficient than the serial type in energy production, whereas the serial-type method produced water with a temperature approximately 47% higher than that of the parallel type. Notably, it was advantageous to apply the parallel-type connection to maximize the energy generation efficiency in buildings where the system efficiency is vital and the serial-type connection in buildings where the high temperature of hot water is required.