Abstract The X‐ray absorption near edge fine structure (XANES) and the extended X‐ray absorption fine structure (EXAFS) associated with the CoK absorption discontinuity are investigated in the pure metal, in the compound CoAsSe and in two other similar trivalent compounds. The analysis of the results obtained enables to obtain the average bond length (Co‐ligand distance) in CoAsSe for which the value is not known from crystallographic work.