Synthesis of organometal halide perovskite CH3NH3PbI3 has received much attention recently because of promising photosensitive properties usable for solid state solar cell (SSSC). Here the crystals of tetragonal phase (I4/mcm, a =8.8743 Å, c =12.6708 Å) of CH3NH3PbI3 were prepared. Formation of the CH3NH3PbI3 crystals was controlled by the SEM, EDS, XRD and Raman spectroscopy. Optical characteristics of the crystals were obtained using PL spectrometry and spectral ellipsometry methods. PL spectra of orthorhombic phase of CH3NH3PbI3 crystals were recorded the first time. Taking into account the practice use, the CH3NH3PbI3 films are obtained via the sol–gel method with “spin-on” coating of CH3NH3PbI3 sol. The films are 500 nm in thickness and exhibit an openwork structure. Such a structure is optimal for SSSC construction because it increases the surface contact area between CH3NH3PbI3 and p-conductor.