Metal/semiconductor photonic crystals (PCs) will be applied in important national defense technology, the research focus of its growth is to how to assemble the PMMA microsphere into colloidal crystal. Based on the well-established vertical deposition method and isothermal evaporation processing, a controllable vertical deposition (CVD) method was developed to prepare the photonic crystal in the study. The highly monodisperse PMMA colloid particles with size of 294 nm and 345 nm were synthesized from the MMA and azo-initiator and assembled into photonic crystals by the technology; it was shown from the SEM observation of the sample that the bulk structure of the crystal has a high periodical array, the perfect order zone is above 20 μm; the surface structure of the crystal is completely flat and has only two defects in the 3 μm×5 μm order zone. It was concluded from the growth interface analysis that during the process of controllable vertical deposition, the crystals grow by continuous growth mechanism and the growing crystals have rough interface.