Vanadium nitride is an important metallurgical additive and a good electrode material. Studying its interior microstructure is necessary for fully understanding its intrinsic nature and for better applications. Two groups of known experimental transition data of low-lying rotational quantum states and the analytical formula derived by Sun group in their previous works are used in this work to predict the high-lying accurate R-branch emission spectra of the (0, 0) band in the f1Φ–a1Δ and d1∑+–X3Δ1 systems of the VN molecule. Theoretical results not only reproduce all known experimental spectral lines accurately, but also generate correct values of the unknown spectral lines up to J=80 that are not available experimentally. This study defines a contribution degree C to measure the contributions of known experimental spectral lines to the predicted line. The contribution degree C makes it easier for one to understand the relationships and influences among the transition lines (rotational states) of the given system.