PbTiO3-based ferroelectrics have impressive electroactive properties, originating from the Pb2+ 6s2 electron lone-pair, which cause large elastic distortion and electric polarization due to cooperative pseudo Jahn-Teller effect. Recently, tin-based perovskite oxide (SnTiO3) containing Sn2+ and a chemistry similar to that of the 6s2 lone-pair has been identified as a thermally stable, environmentally friendly substitute for PbTiO3-based ferroelectrics. However experimental attempts to stabilize Sn2+ on the A-site of perovskite ATiO3 have so far failed. In this work, we report on the growth of atomically smooth, epitaxial, and coherent Sn-alloyed SrTiO3 films on SrTiO3 (001) substrates using a hybrid molecular beam epitaxy approach. With increasing Sn concentration, the out-of-plane lattice parameter first increases in accordance with the Vegard’s law and then decreases for Sn(Sr+Ti+Sn) at. % ratio > 0.1 due to the incorporation of Sn2+ at the A-site. Using a combination of high-resolution X-ray photoelectron spectroscopy and density functional calculations, we show that while majority of Sn is on the B-site, there is a quantitatively unknown fraction of Sn being consistent with the A-site occupancy making SrTiO3 polar. A relaxor-like ferroelectric local distortion with monoclinic symmetry, induced by A-site Sn2+, was observed in Sn-doped SrTiO3 with Sn(Sr+Ti+Sn) at. % ratio = 0.1 using optical second harmonic generation measurements. The role of growth kinetics on the stability of Sn2+ in SrTiO3 is discussed.