The chemical bonding and local order in Si, Si‐N, Si‐C, and Si‐C‐N nanometric powders prepared by laser synthesis have been investigated by using two experimental methods. The local environment of Si, C, and N atoms have been studied by x‐ray‐induced photoelectron spectroscopy, from a detailed analysis of the Si 2p, C 1s, and N 1score levels. Complementary information concerning the structural arrangement around Si atoms has been deduced from extended x‐ray‐absorption fine‐structure analysis performed at the SiKedge. The results show that the Si and Si‐C powders prepared with a 600 W laser power are pure, well‐crystallized materials; the Si‐N sample prepared with the same laser power has a disordered structure, although chemical order exists. For the composite samples, the results reveal that, in particular preparation conditions, a local C‐Si‐N3structure is formed.