In this work, enhanced optoelectronic properties of SnS is attained through the substitutional doping of Bi into the SnS lattice at the ‘Sn’ sites by following cost effective solvothermal method at a reaction temperature of 170 °C for a duration of 90 min. The charge states explored through XPS analysis revealed the existence of the constituent elements in Sn2+, S-Sn2+ and Bi3+ states. The chemical structure investigated through Raman analysis revealed the successful doping of Bi into orthorhombic SnS without affecting its phase purity for doping up to 12 %. With increasing the doping up to 4 %, (a) the shift in 2θ peak position to the higher angle side and the contraction in unit cell volume as evident from XRD analysis ensured the substitutional doping of Bi3+ into Sn2+ sites and (b) the direct energy band gap and electrical resistivity are reduced from 1.60 to 1.30 eV and 719×103 to 627×102 Ω cm respectively and the carrier concentration is enhanced from 1.22×1012 to 8.92×1013 cm−3 revealing the optimum doping of Bi into SnS is 4 %. Due to the effect of doping, the homogeneity in size and shape of the nanorods is enhanced with an increase in size as evident from HR-TEM analysis. The electrical transport properties obtained from Hall measurement studies showed p-type conductivity for SnS with Bi doping up to 10 %. Hence, this report provides the first experimental confirmation for the absence of any carrier polarity conversion in phase pure SnS due to the incorporation of Bi.