Porous silicon materials have been shown to have bright prospects for applications in light emitting, solar cell, as well as light- and chemical-sensing devices. In this report, structures of porous silicon prepared by anodic etching in HF-based solution with various etching times were studied in detail by Atomic Force Microscopy and Small Angle X -ray Scattering technique using the high energy beam line at Pohang Light Source in Korea. The results showed the coexistence of the various pores with nanometer and submicrometer scales. For nanameter size pores, the mixed ones with two different shapes were identified: the larger ones in cylindrical shape and the smaller ones in spherical shape. Volume fractions of the cylindrical and the spherical pores were about equal and remained unchanged at all etching times investigated. On the whole uniform values of the specific surface area and of the size parameters of the pores were observed except for the larger specific surface area for the sample with the short etching time. The results implies that etching process causes the inner surfaces to become smoother while new pores are being generated. In all SAXS data at large Q vectors, Porod slope of -4 was observed, which supports the fact that the pores have smooth surfaces.