This work presents the first investigation on the intermolecular potential energy surface of the ground electronic state of the O-2(-)((2)Pi(g))-H-2((1)Sigma(+)(g)) complex. High level correlated ab initio calculations were carried out using the Hartree-Fock spin unrestricted coupled cluster singles and doubles including perturbative triples correction [RHF-UCCSD-(T)]/aug-cc-pVXZ levels of calculations, where XZ = DZ, TZ, QZ, and SZ. Results of full geometry optimization and the intermolecular potential energy surface (IPES) calculations show four equivalent minimum energy structures of L-shaped geometry with C-s symmetry at (De) was calculated calculated as equilibrium along the (2)A '' surface of the complex. For these equilibrium minimum energy structures, the most accurate value for the dissociation energy 1407.7 cm(-1), which was obtained by extrapolating the counterpoise (CP) corrected De values to the complete basis set (CBS) limit. This global minimum energy structure is stabilized by an ion-induced-dipole hydrogen bond. Detailed investigations of the IPES show that the collinear structure is unstable, while the C-2v geometries present saddle points along the (2)A '' surface. The barrier height between the two equivalent structures that differs in whether the hydrogen-bonded hydrogen atom is above or below the axis that connects centers of masses of the H-2 and O-2(-) moieties within the complex was calculated as 70 cm(-1). This suggests that the complex exhibits large amplitude motion. The barrier height to rotation of the H-2 moiety by 180 degrees within the complex is 1020 cm(-1). Anharmonic oscillator calculations predicted a strong H-H stretch fundamental transition at 3807 cm(-1). Results of the current work are expected to stimulate further theoretical and experimental investigations on the nature of intermolecular interactions in complexes that contain the superoxide radical and various closed-shell molecules that model atmospheric and biological molecules. These studies are fundamental to understanding the role of the 02 anion in chemistry in the atmosphere and in biological systems.