The porous Si (PS) was annealed at various temperature in air, argon, and nitrogen atmosphere. Structural and optical properties of the annealed PS were investigated by scanning electron microscopy (SEM) and photoluminescence (PL). It is found that the shape of pore is changed from circle to channel as increasing annealing temperature which was annealed in air and argon atmosphere. In case of PS annealed in nitrogen atmosphere, the shape of pore is changed from channel to circle with increase annealing temperature from 600 to 800℃. The PL peak position is blue-shifted with increasing annealing temperature. As annealing temperature increases, the PL intensity of the PS annealed in argon is decreased but that of the PS annealed in nitrogen is increased. It might be due to the formation of SiN bonds and it passivates the non-radiative centers which is Si dangling bonds on the surface of the PS.