Optical constants and band structure of InxGa1–xP1–yNy lattice matched to GaP (100) substrate are investigated. Nitrogen concentration in the film estimated by X‐ray diffraction and X‐ray photoelectron spectroscopy, was 1.4%, 1.8% and 3.5%. Refractive index and transition critical points E0 (Γv to Γc), E1 (Lv to Lc) and E2 (Xv to Xc) are evaluated by spectroscopic ellipsometry. When N composition increases from 1.4% to 3.5%, both photoluminescence (PL) peak energy, EPL, and E0 shift to lower energy, and the energy difference ΔE = E0 – EPL decrease from 380 meV to 110 meV. The large red‐sift of EPL from the E0 suggest that the luminescence is of defect‐related luminiscence, and crossover point of indirect band structure estimated by the extrapolation of N‐composition dependence of ΔE is estimated to be arroud in In0.1Ga0.9P0.96N0.04. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)