In the present paper we report structural, optical, morphological and electrical properties of thin films of MoBi2S5 prepared by facile self organized arrested precipitation technique (APT) from aqueous alkaline bath. X-ray diffraction study on thin films suggests orthorhombic and rhombohedral mixed phase structure. The samples are further annealed under vacuum at 373 and 473 K. The EDS pattern shows minor loss of sulphur upto 473 K. The optical absorption in visible region shows direct allowed transition with band gap variation over 1.2-1.1 eV. Post-heat treated samples exhibit n-type electrical conductivity. SEM images show uniform distribution of spherical grains with diameter similar to 200 nm for as-synthesized MoBi2S5 thin film. The grain size increases with annealing temperature and morphology becomes more compact due to crystallization of thin film. The surface roughness deduced from AFM, was in the range of 1.29-1.92 nm. The MoBi2S5 thin films are employed for the fabrication of photoelectrochemical solar cells as all the samples exhibit strong absorption in visible to near IR region. Due to vacuum annealing it gives a significant enhancement of power conversion efficiency (eta) upto 0.14% as compared to as-synthesized MoBi2S5 thin film. (C) 2014 Elsevier B.V. All rights reserved.