Ge-substitution dependence of the structural, electronic, and magnetic properties for Ge x NFe 4−x (0.0 ≤ x ≤ 1.0) compounds has been investigated systematically. An obvious structural phase transition from Pm3m to I4/mcm around x = 0.5 is observed by substitution-dependent X-ray diffractions. The modified lattice constants a′ = a/2 1/2 and c′ = c/2 are used to depict the specific structure for tetragonal GeNFe 3 . Especially, the tetragonal structure exhibits an expansion along the direction of the c axis compared with the cubic γ′-Fe 4 N; also, the sublattice of the octahedral structure around N atoms is stretched along the tetragonal [001]. As a consequence of increasing substitution, lower ferromagnetic (FM) to paramagnetic transition temperature is associated with the tetragonal GeNFe 3 (T C ≈ 90 K). The much higher magnetization (M s ) of γ′-Fe 4 N than that of GeNFe 3 can be attributed to the FM and ferrimagnetic ground states, respectively, which are confirmed by the density functional theory calculations. The average magnetic moment for GeNFe 3 is about 0.446 μ B /atom per formula unit based on the calculations, which is approximately similar to the experimental value. Our calculations determine that the electrons of Fe-3d contribute the dominant role among the total density of states, and Ge-4p and N-2p are mainly contributed away from the Fermi energy (E F ).