A computational and X-ray crystallographic investigation of the electronic and geometric structures of a range of sulfonyl (-SO(2)-) and phosphonyl (-PO(2)--) containing species was undertaken to investigate the nature of valency and bonding in these functional groups. The traditional representation of sulfonyl and phosphonyl species is with octet-violating Lewis structures, which require d-orbital participation at the central atom. However, computational studies cast serious doubt upon this bonding model. In this work, we have employed NBO/NRT analysis to investigate hybridization, atomic formal charges, donor-acceptor interactions, and resonance structure contributions. Our results predict that within sulfonyl and phosphonyl systems, bonding interactions are highly polarized, of the form X+-Y- (X = P, S), and possess additional contributions from reciprocal n --> sigma* interactions where substituents off sulfur or phosphorus simultaneously act as donors and acceptors. Experimental evidence for the proposed bonding arrangement is provided for the sulfonyl functional group through a series of low-temperature X-ray structure correlations for sulfate monoesters, sulfamates, and methanesulfonates. Examination of changes to bond lengths and geometries upon substituent variation support the computational results. Together, our studies lend support for a bonding network in sulfonyl and phosphonyl groups composed of polar interactions augmented with reciprocal hyperconjugative bonding, which does not necessitate significant d-orbital participation nor formal octet violation at the central sulfur or phosphorus.