The concept of hybrid orbitals is one of the key theoretical concepts used by chemists to explain the structures and other properties of molecules. Recent work found that the hybrid orbitals from modern ab initio valence bond wave functions differ significantly from traditional hybrid orbitals. We report a detailed analysis of the orbitals of methane, ethylene, and acetylene from spin-coupled generalized valence bond (SCGVB) wave functions, a variationally optimized valence bond wave function that places no constraints on the orbitals and spin function. The carbon-centered orbitals in the SCGVB wave functions are found to be 2s−2p hybrid orbitals largely localized on the carbon atom and pointed directly at the hydrogen atoms to which they are bonded. However, the SCGVB orbitals for methane, ethylene, and acetylene differ markedly from the sp3 , sp2 , and sp hybrid orbitals traditionally associated with these molecules. It is now clear that the orbitals in modern valence bond wave functions do not follow the hybridization rules of traditional valence bond theory. These findings imply that, in modern valence bond theories, other factors are responsible for the structures and properties of molecules that are traditionally attributed to orbital hybridization.