The magnetoelectric (ME) and multiferroic (MFs) materials are emerging and appealing class of material with huge potential to be employed as photoactive materials for converting the photon energy into the electrical energy. The co-existence of both ferroelectricity and magnetism simultaneously in the single and composite phase preferable at room temperature is the major factor for their application in the photovoltaic (PV) field. The coupling of the optical properties with the present ferroic properties has made huge progress and revolutionized the PV research. The bulk PV effect which is primarily observed in the ferroelectric materials results in the smooth charge carrier separation based on remnant polarization and makes possible to deliver the above bandgap photo-voltage. Here, it is attempted to understand the Shockley–Queisser (SQ) limit and quantum efficiency (internal and external) and the mechanism involved in the ME effect. Further, the possible green energy application of the ME-MF material is also discussed.