Type-II staggered band aligned layered nanohybrids (LNHs) satisfy the unique characteristics required for photocatalysts. Here, the spin-assisted layer-by-layer deposition (SA-LBL) of stibnite/reduced graphene oxide (Sb2S3/rGO) LNHs are fabricated and their structural, morphological, electrical, and optical properties are reported. From the FESEM analysis, it was found that with increasing rGO content, the morphology of Sb2S3 nanoparticles changed from the granular to nanorods which might be due to Ostwald ripening or microstructural coarsening effect. Further, Raman spectroscopy proves that the B1 g and Ag of Sb2S3 decrease by the addition of rGO mainly due to the electron-phonon interaction. Based on the estimation of valence band edge and conduction band edge of Sb2S3/rGO LNHs using X-ray photoelectron spectroscopy and optical studies, we propose that the interface in Sb2S3/rGO LNHs is a type-II staggered band alignment Direct Z-scheme. The increased spatial charge separation and carrier lifetime of Sb2S3/rGO LNHs materials results in opening a new pathway to explore and extend their applications as photocatalysts.