Dye sensitization is a fundamental function for solar cell and silver halide (AgX) microcrystal to increase the optoelectronic conversion efficiency. In this paper, the spectral properties and self-assembled structure of three types of cyanine dyes, adsorbed both on (100) surface of 0.4 μm AgBr cubic crystal and (111) surface of 1.8 μm AgBr tabular crystal, were studied with combination ofspectroscopy and atomic force microscopy (AFM) technique. Rectangular aggregation structure is formed on the crystal faces of (100) and (111) for both anionic and cationic dyes, while herringbone-stacking structure is formed by anionic-cationic dye, and a J-band spectrum is correspondingly detected. The photoelectron property of dye-sensitized samples was also investigated with microwave absorption and dielectric spectrum detection technology. After excited by a 355 nm fast-pulse laser, the photoelectron decay process of anionic-cationic dye sensitized sample is the fastest. This indicates that the affection of anionic-cationic dye aggregates to the photoelectron decay is the biggest, and the sensitization is more efficient.