Extended X-ray absorption fine structure (EXAFS) has been used to investigate the local bonding structure in several pseudobinary semiconductor alloy systems,(A_1-xB_x)C. Both cation- and anion-substituted pseudobinary alloys with x ranging from 0 to 1 were studied. It is found that the first neighbor cation-anion distance remains closer to that in the pure binary compound than to that of the average or virtual crystal distance, determined from the lattice constant, despite a large difference between the two. Some change in bond length with composition, however, does occur, but it corresponds to only 20–25% of the change predicted in the virtual crystal approximation. These results agree well with the predictions of recent theories. The second-neighbor structural results indicate that these alloys are solid solutions with negligible clustering. Also these bulk samples prepared at high temperatures have occupation of the mixed sublattice that is consistent with that of a random distribution. This differs from the ordered distributions observed for samples grown under special conditions.