In the present work, the pyroelectric properties of Sn‐doped BaTiO3 (BaTi1‐xSnxO3) were investigated. A significant increase in pyroelectric coefficient was observed for x = 0.05 composition and found to be 10 × 10−4 C/m2 K at 350 K. Further, the pyroelectric figure of merits (FOMs) for current responsivity (Fi), voltage responsivity (Fv), and energy harvesting (Fe and ) were calculated for all investigated samples. A large improvement in FOMs was achieved for x = 0.05 compared with undoped ceramic. BaTi1‐xSnxO3 (x = 0.05) was subjected to further pyroelectric analysis revealing an open‐circuit voltage of 0.6 V when it was exposed to temporal temperature gradient. The voltage and current were also measured across resistances 100 kΩ, 1 MΩ, and 5 MΩ. The results reveal that BaTi0.95Sn0.05O3 will be one of the potential lead‐free pyroelectric materials.