Two chemical vapor transport methods with Zn(NH4)3Cl5 transport agent were developed to grow ZnSe bulk single crystals. Two kinds of Zn-rich ZnSe single crystals, conical crystal and flake crystal，were grown directly from untreated ZnSe polycrystals and two elements, respectively. The structure characters, purity and etch pit density were studied by rotating orientation XRD, PL spectrum and optical microscope. The contrastive investigation between two growth results indicated that the conical crystal was composed of (111) and (100) faces, and the flake crystal exhibited only (111) face. Moreover, the vicinal interface leaning to (111) face by the angle of 3.1° was the dominative growth face in vapor growth system, and growth occurs by layer-by-layer model. FWHM of RO-XRD pattern of ZnSe (111) face was 24sec for conical ZnSe crystal and 48s for ZnSe flake crystal. The results suggested that high-quality ZnSe crystals can be grown from the chemical vapor transport method with Zn(NH4)3Cl5 transport agent.