The static first hyperpolarizability of the van der Waals CH4N2 complex was calculated. The calculations were carried out in the approximation of the rigid interacting molecules for a broad range of intermolecular separations (R = 6–40 a0) and for six configurations at CCSD(T) level of theory using the correlation consistent aug‐cc‐pVTZ basis set with the basis set superposition error correction. It was shown that the long‐range classical approximation, including the terms up to R−6, is in a good agreement with ab initio calculations for R > 11 a0. It was found out that for the family of most stable configurations of the complex, the first hyperpolarizability invariants practically do not change (the changes are less than 0.1%). Under forming the stable van der Waals CH4N2 complex, the intensity and degree of depolarization of the hyper‐Rayleigh scattering are noticeable decreased (by ∼10%) to be compared with the free CH4 and N2 molecules. © 2012 Wiley Periodicals, Inc.