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The functional properties of polyvinyl pyrrolidone/polyvinyl alcohol (PVP/PVA) blend incorporated with non-stoichiometric tin sulphide (SnS) have been explored for optoelectronic devices. PVP/PVA blend incorporated with non-stoichiometric Sn/S ratios (1:0.8–1:1.2) of 1.0 wt.% SnS were prepared by casting method. The effect of the non-stoichiometric Sn/S ratio of SnS on the structure, optical and photoluminescent (PL) properties of the composite was examined by Fourier transform infrared, UV-visible-NIR and photoluminescence spectrophotometers. The optical band gap energy decreases, while Urbach energy increases via SnS incorporation. The lattice dielectric constant is improved about three times, while the free carriers’ concentration to the effective mass is enhanced by one order of magnitude due to SnS1.2 incorporating. PL measurements reveal that PVP/PVA blends incorporated with SnS could emit spectra in the visible region. Designing the optical and photoluminescent properties of the PVP/PVA blend reveal their role in advanced optoelectronic devices.