The structure and interface characteristics of (LaVO3)6m(SrVO3)m superlattices deposited on (100)-SrTiO3 (STO) substrate were studied using Transmission Electron Microscopy (TEM). Cross-section TEM studies revealed that both LaVO3 (LVO) and SrVO3 (SVO) layers are good single crystal quality and epitaxially grown with respect to the substrate. It is evidenced that LVO layers are made of two orientational variants of a distorted perovskite compatible with bulk LaVO3 while SVO layers suffers from a tetragonal distortion due to the substrate induced stain. Electron Energy Loss Spectroscopy (EELS) investigations indicate changes in the fine structure of the V L23 edge, related to a valence change between the LaVO3 and SrVO3 layers.