The ZnSe sample grown by chemical bath deposition (CBD) method were annealed in Ar gas at 450 C. Using extrapolation method of X-ray diffraction pattern, it was found to have zinc blend structure whose lattice parameter a, was 5.6687 Å. From Hall effect, the mobility was likely to be decreased by impurity scattering at temperature range from 10 K to 150 K and by lattice scattering at temperature range from 150 K to 293K. The band gap given by the transmission edge changed from 2.7005 eV at 293 K to 2.8739 eV at 10 K. Comparing photocurrent peak position with transmission edge, we could find that photocurrent peaks due to excition electrons from valence band, Γ_8 and Γ_7 to conduction band Γ_6 were observed at photocurrent spectrum. From the photocurrent spectra by illumination of polarized light on the ZnSe thin film, we have found that values of spin orbit coupling splitting Δ so is 0.098 eV. From the PL spectra at 10 K, the peaks con-esponding to free hound excitons and D-A pair and a broad emission band due to SA is identified. The binding energy of the free excitons are determined to be 0.0612 eV and the dissipation energy of the donor -bound exciton and acceptor-bound exciton to be 0.0172 eV, 0.0310 eV, respectively.