The integration of photovoltaic technologies into greenhouse envelopes appears to be an innovative and environmentally-friendly way to supply their various energy demands. However, the effect on the inner growing conditions, especially on the temperature, must be assessed in order to effectively implement this solution. In this study, experimental temperature data were obtained over two years for four structures built with different photovoltaic technologies (mono-crystalline silicon, amorphous silicon, cadmium telluride, and an organic polymeric technology) and fitted to a thermal model in order to provide a comprehensive analysis of their potential utilization as a cover material in greenhouses. Additionally, the thermal effect of color in structures composed of several common construction materials (brick, wood, plasterboard and glass) was quantified and modelled, supplementing the thermal analysis of passive solutions for this application. In all cases, inner and ambient temperature differences of up to +20 °C, created by a passive heating effect during the day, and −5 °C, created by a passive cooling effect during the night, have been observed, suggesting the use of the photovoltaic modules with different degrees of structure coverage, complemented with the color tuning of the modules themselves as passive methods to control the temperature and light spectrum of greenhouses.