We demonstrate ultrafast shifting of a photonic stop band driven by a photoinduced phase transition in vanadium dioxide (VO 2 ) forming a three-dimensional photonic crystal. An ultrashort 120-fs laser pulse induces a phase transition in VO 2 filling the pores of an artificial silica opal, thus changing the effective dielectric constant of the opal. Consequently, the spectral position of the photonic stop band blue-shifts producing large changes in the reflectivity. The observed switching of the photonic crystal is faster that 350 fs. The demonstrated properties of opal-VO 2 composite are relevant for potential applications in all-optical switches, optical memories, low-threshold lasers, and optical computers.