Lead-free perovskite solar cells (PSCs) have attracted interest among scientists searching for eco-friendly energy harvesting devices. Herein, the effects of ozone exposure on poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PE-DOT:PSS) in lead-free tin halide PSCs as a facile and low-cost process for improving device performance are analyzed. Two types of tin-based PSCs and one typical lead-based PSC were fabricated. The ozone exposure on PEDOT:PSS increases the short-circuit current density (J SC ) and the fill factor (FF) of PSCs in all cases with perovskite grain enlargement and hole-mobility enhancement of the devices, respectively. For open-circuit voltage (V OC ), the outcome depends on the band gap and the energy levels of the perovskite films. While ozone exposure treatment is favorable for PEA 0.15 FA 0.85 SnI 3 -based tin PSCs, V OC decreases with ozone exposure in the case of Ge:EDA 0.01 FA 0.98 SnI 3 -based tin PSCs because of a misalignment of the energy levels. Regardless, the efficiency of PEA 0.15 FA 0.85 SnI 3 -based tin PSCs increases from 8.7 to 10.1% when measured inside a glovebox upon ozone exposure of PEDOT:PSS. The efficiency of Ge:EDA 0.01 FA 0.98 SnI 3 -based tin PSCs increases from 6.8 to 8.1%, and the devices retain an efficiency of 5.0% even after 50 days in air.