The increasing environmental pollution generated by the conventional sources of energy and the crises created via extensive use of fossil fuels, especially global warming, forces humanity to develop innovative technologies to utilize renewable and sustainable energy sources such as solar radiation. The present efficiency of conventional silicon-based bipolar heterojunctions used in solar panels, could be improved employing the potential of the photovoltaic properties of multiferroic materials in novel polarization driven carrier-based devices. In a span of a few years, the multiferroic films are in the center of attraction of researchers in the field of solar energy conversion due to their excellent efficiency of ferroelectric polarization-driven carrier separation, possible magnetism-photon coupling, and the high yield of the photo-voltage above the band-gap. In this featured letter, the focus is on critically reviewing the advances on multiferroic structure, new possibilities in this direction and future scopes and challenges for their role in increasing the photovoltaic response via interfacial engineering and band-gap tuning..