The structure of Vertical-Cavity Surface-Emitting Lasers (VCSEL) has been grown on (100)2° off toward <111>A n-GaAs(Si) substrate by MBE. The numbers of reflectors in top and bottom Distributed Bragg Reflector (DBR) structures are 24.5 pairs and 34.5 pairs, respectively. The high quality VCSEL structure is characterized by PL, SEM and X-ray double crystal diffraction (XRD). The peak wavelength of PL spectrum is 837.0 nm and the FWHM is 28.9 nm at room temperature. The structure parameters of VCSEL are obtained from the rocking curve. The first and second satellite peaks around the main (“0” level) reflection peak appear in the rocking curve. The FWHM of diffraction peaks of “0” level and GaAs substrate are 12.56″ and 11.79″, respectively, which are quite close, showing much higher integrity of the crystal lattice. The experimental results show that the resonant wavelength of cavity modes (837.2 nm) and the peak wavelength of PL spectrum are well matched.