The power conversion efficiency (PCE) of single-junction solar cells was theoretically predicted to be limited by the Shockley-Queisser limit due to the intrinsic potential loss of the photo-excited electrons in the light absorbing materials. Up to now, the optimized GaAs solar cell has the highest PCE of 29.1%, which is close to the theoretical limit of ~33%. To pursue the perfect photovoltaic performance, it is necessary to extend the lifetimes of the photo-excited carriers (hot electrons and hot holes) and to collect the hot carriers without potential loss. Thanks to the long-lived hot carriers in perovskite crystal materials, it is possible to completely convert the photon energy to electrical power when the hot electrons and hot holes can freely transport in the quantized energy levels of the electron transport layer and hole transport layer, respectively. In order to achieve the ideal PCE, the interactions between photo-excited carriers and phonons in perovskite solar cells has to be completely understood.