Organic-inorganic hybrid perovskite solar cells (PSCs) continue to attract considerable attention due to their excellent photovoltaic performance and low cost. In order to realize the fabrication of PSCs on temperature-sensitive substrates, low-temperature processing of all the components in the device is required, however, the majority of the high-performance PSCs rely on the electron transport layers (ETLs) processed at high temperatures. Herein, we apply excimer laser annealing (ELA) to treat ETLs (Ga-doped ZnO, GZO) at room temperature. A synergetic improvement in optical transparency and electrical conductivity is achieved after ELA treatment, which in turn improves light absorption, enhances electron injection, and depresses charge recombination. Devices fabricated with ELA treated GZO ETL acheived a power conversion efficiency (PCE) of 13.68%, higher than that of the PSCs utilizing GZO with conventional high-temperature annealing (12.96%). Thus, ELA is a promising technique for annealing ETLs at room temperature to produce efficient PSCs on both rigid and flexible substrates.