We have used an experimental strategy that, combining nuclear reaction analysis and Rutherford backscattering spectrometry both in random and channeling geometry, allowed an accurate quantification of the total amount of N in InxGa1−xNyAs1−y/GaAs and GaNyAs1−y/GaAs epitaxial systems (0.038<x<0.044, 0.015<y<0.045), and a precise localization of nitrogen atoms into the lattice. All N atoms were found on substitutional positions. This information was then exploited to correlate the relaxed lattice parameter of the epilayers obtained by high-resolution x-ray diffraction to the N concentration, by taking into account the elasticity theory, allowing a verification of the validity of Vegard’s rule in the whole range of investigated N concentrations for both alloys. The effect of N incorporation on the lattice parameter has been found to be the same both for ternary and quaternary alloys.