The formation and destruction of O3 within the Chapman cycle occurs as a result of inelastic collisions with a third body. Since N2 is the most abundant atmospheric molecule, it can be considered as the most typical candidate when modeling energy-transfer dynamics. We report a new ab initio potential energy surface (PES) of the O3-N2 van der Waals complex. The interaction energies were calculated using the explicitly correlated single- and double-excitation coupled cluster method with a perturbative treatment of triple excitations [CCSD(T)-F12a] with the augmented correlation-consistent triple-zeta aug-cc-pVTZ basis set. The five-dimensional PES was analytically represented by an expansion in spherical harmonics up to eighth order inclusive. Along with the global minimum of the complex (De = 348.88 cm−1), with N2 being perpendicular to the O3 plane, six stable configurations were found with a smaller binding energy. This PES was employed to calculate the bound states of the O3-N2 complex with both ortho- and para-N2 for total angular momentum J = 0 and 1, as well as dipole transition probabilities. The nature of the bound states of the O3-oN2 and O3-pN2 species is discussed based on their rovibrational wave functions.