AbstractStrongly correlated manganites can be considered as model systems for the study of photovoltaic harvesting of hot polarons that can be excited from the electronically ordered ground state. In order to gain basic understanding of hot polaron harvesting, the deviations of the photovoltaic response of a heterojunction with polaronic absorber from a conventional semiconductor are analyzed. Specifically, the spectral and photon power density dependence of the open circuit voltage Uoc and the short circuit current density Jsc in heterojunctions consisting of orbital ordered Pr1‐xCaxMnO3 (x = 0.1, PCMO) thin films epitaxially grown on single crystalline (100) SrTiO3 (STO) and Nb‐doped (100) SrTiO3 (STNO) substrates are investigated. The observed behavior is fundamentally different from conventional solar cells, in which Uoc is limited by fast carrier relaxation to the band edges. Whereas the spectral and photon power dependence of Uoc of conventional semiconductor junctions is well described by the Shockley‐Queisser (SQ) theory, the hot polaron junctions surprisingly show a scaling law behavior of Uoc. Such scaling laws otherwise apply to equilibrium order parameters in second‐order phase transitions. It is concluded that its physical origin is the unique dependence of the quasi‐Fermi level splitting on temperature, photon energy, and power density in a hot polaron system.