Due to exciting catalytic activity and selectivity, tailoring of nano catalysts consisting of preferred crystal facets and desired structural properties remains at the forefront of materials engineering. A facile one-step nonhydrolytic solvothermal synthesis of a nanocomposite of reduced graphene oxide and one-dimensional nitrogen-doped Nb2O5 (N-NbOx) with exposed (001) facet is described. Triethylamine performed the dual role as nitrogen source and capping agent to control the size and unidirectional growth of Nb2O5 nanocrystallites. The nano composite showed efficient visible-light-mediated (lambda >420 nm) water splitting in a photoelectrochemical cell. A plausible mechanism for the formation of N-NbOx nanorods and improved photoelectrochemical efficacy in terms of their oriented growth is proposed.