In this work, the efficiency of lead‐free La2NiMnO6 (LNMO)‐based double perovskite solar cells is optimized using solar cell capacitance simulator (SCAPS‐1D). Herein, the device performance is boosted by using different combinations of electron‐transport layers, hole‐transport layers, absorber layer thickness, acceptor doping density, acceptor defect density, and bandgap tuning, and by modifying the electron affinity. To make the device more realistic, the performance of the proposed device is carefully modified in the presence of interface defect density ≈10−13 cm−3, series resistance ≈1 Ω cm2, and shunt resistance ≈6000 Ω cm2, respectively. From the findings, the optimized device exhibits a record open‐circuit voltage = 1.23 V, short‐circuit current density = 27.18 mA cm−2, fill factor = 87.14%, and power conversion efficiency = 29.20% for FTO/SnO2/LNMO/MoO3/Au configuration. Finally, the device performance is tested under different working temperatures, and 300 K is found as the best temperature for the device.