Facile process for the fabrication of multi-layer graphene thin film (MLGF) is reported here. Multi-layer graphene dispersion prepared by liquid-phase exfoliation of graphite was sprayed on a glass substrate by spray pyrolysis method. The structural, optical and electrical properties of the deposited MLGF are investigated. The sheets of graphene are deposited uniformly on the substrate and distribution of small graphene sheets with size of 300–500 nm can be observed in SEM image. AFM and micro-Raman results ensured that the spray-coated graphene thin film is composed of multi-layer graphene sheets. Spray coated graphene thin film showed significant optical transparency of 57% in the visible region (400–550 nm). MLGF possessed the electrical conductivity in the order of 744 S/m with surface resistivity of 3.54 k Ω/sq. The prepared liquid-phase exfoliated graphene thin film showed superior photoelectric response. The results of this study provided a framework for fabricating an optimized MLGF using a spray pyrolysis route for optoelectronics devices.