The binder-free polycrystalline nanostructured molybdenum disulfide (MoS2) films are synthesized on glass substrates placed at 15, 16 and 17 cm with respect to source material by powder vapor transport technique. The X-rays diffraction analysis confirms the development of different diffraction planes related to MoS2 and Mo2S3 phases. The formation of surface morphologies (nano-boxes and nano-fibers) of MoS2 films is associated with increasing substrate distances. The changes in reflectance (0.18–0.09), refractive index (2.52–1.91), energy band gap (1.62–2 eV), Urbach energy (0.61–1.11 eV), dielectric constant (7-5.6), dissipation factor (0.04–0.06), surface/volume energy loss functions (0.0017–0.005/0.002–0.005), optical & electrical conductivities (1.23–2.04 × 1014 s−1 and 9.86–6.70 × 1019 S m−1), single oscillator energy (5.70–3.36 eV), dispersion energy (26.45–5.80 eV), nonlinear and static refractive index (0.041–1.58 × 10−5, 5.64–2.72), linear & nonlinear optical susceptibilities (0.37–0.14 and 0.011–6.16 × 10−6) are strongly associated with increasing substrate distances. Results indicate that the synthesized MoS2 films can be used in optoelectronic and solar cell devices.