Layer structured orthorhombic MoO3-x (alpha-MoO3-x) thin film with low resistivity of about 5 Omega.cm was obtained on glass substrate via conducting a two-step annealing treatment on the thin film deposited by thermal evaporation method. The first step annealing in air enables the formation of a-phase and layered structure, while the second step annealing in N-2 gives rise to low resistivity without deteriorating crystal structure. Finally, this two-step annealing treatment empowers the formation of alpha-MoO3-x thin film on indium tin oxide (ITO) substrate, providing layer structured alpha-MoO3-x/ITO bilayer electrode for organic light emitting diode and thin film solar cells.