As the world strives toward its net‐zero targets, innovative solutions are required to reduce carbon emissions across all industrial sectors. One approach that can reduce emissions from food production is agrivoltaics—photovoltaic devices that enable the dual‐use of land for both agricultural and electrical power‐generating purposes. Optimizing agrivoltaics presents a complex systems‐level challenge requiring a balance between maximizing crop yields and on‐site power generation. This balance necessitates careful consideration of optics (light absorption, reflection, and transmission), thermodynamics, and the efficiency at which light is converted into electricity. Herein, real‐world solar insolation and temperature data are used in combination with a comprehensive device‐level model to determine the annual power generation of agrivoltaics based on different photovoltaic material choices. It is found that organic semiconductor‐based photovoltaics integrated as semitransparent elements of protected cropping environments (advanced greenhouses) have comparable performance to state‐of‐the‐art, inorganic semiconductor‐based photovoltaics like silicon. The results provide a solid technical basis for building full, systems‐level, technoeconomic models that account for crop and location requirements, starting from the undeniable standpoint of thermodynamics and electro‐optical physics.