Sustainable food and energy supply on limited agricultural land is a major challenge under the growing global population. The current large-scale plastic-covered traditional greenhouses ensure the stability of crop yield and quality throughout the year. However, traditional greenhouses rely on fossil fuel or grid electricity input. Agrivoltaic greenhouse systems, as a new technology, can reduce fuel and grid electricity consumption, but photovoltaic conflicts with photosynthesis because both use solar energy as input energy. Organic photovoltaic (OPV) is unique. It has wavelength-selective absorption spectra and excellent flexibility. Therefore, a match between OPV and the plastic-covered traditional greenhouse is inevitable. This overview focuses on the opportunities and advantages of OPV in the agrivoltaics area, and assess the economic viability of OPV agrivoltaic systems. In addition, challenges to OPV implementation in agrivoltaic systems are also discussed, including OPV technology, agronomic management and crop selection. This study digs into the innovative application of OPV agrivoltaic technology and demonstrates the technology’s enormous potential.