AbstractThe molecular radicals, systems with unpaired electrons of open‐shell electronic structures, set the stage for a multidisciplinary science frontier relevant to the cooperative magnetic exchange interaction and magnetoelectric effect. Here ferroelectricity together with magnetic spin exchange coupling in molecular radical hydrocarbon solids is reported, representing a new class of magnetoelectrics. Electronic correlation through radical–radical interactions plays a decisive role in the coupling between magnetic and charge orders. A substantial photoconductance and visible‐light photovoltaic effect are found in radical hydrocarbons. The ability to simultaneously control and retrieve the changes in magnetic and electrical responses opens up a new breadth of applications, such as radical magnetoelectrics, magnets, and optoelectronics.