Significantly slow hot-carrier-cooling happens in a multiphase quasi two-dimensional (2D) perovskite film of (BA) 2 (FA) n−1 Pb n I 3n+1 , where BA is butylammonium, FA is formamidinium, and n = 3 nominally. Due to this phenomenon, a linearly polarized multi-peak emission from phases of n = 2, 3, and 4 emerges and the ever-present one from n = ∞ phase blueshifts in the photoluminescence (PL) spectra, excited using a nanosecond pulsed laser with increasing excitation intensities. Furthermore, hot-carrier PL from small n materials also emerges using a continuous wave laser with an intensity of ∼100 mW/cm 2 ; consequently, the abnormal enhancement of the open-circuit voltage through hot-carrier extraction above 300 mW/cm 2 is achieved. Our work may prove that the FA-based 2D perovskite gives a direction to fabricating hot-carrier solar cells that potentially boost the power conversion efficiency.