We report a structural study of molecular beam epitaxy-grown lattice-matched GaP/Si(0 0 1) thin layers with an emphasis on the interfacial structural properties, and optical studies of GaAsP(N)/GaP(N) quantum wells coherently grown onto the GaP/Si pseudo substrates, through a complementary set of characterization tools. Room temperature photoluminescence at 780 nm from the (GaAsPN/GaPN) quantum wells grown onto a silicon substrate is reported. Despite this good property, the time-resolved photoluminescence measurements demonstrate a clear influence of non-radiative defects initiated at the GaP/Si interface. It is shown from simulations, how x-ray diffraction can be used efficiently for analysis of antiphase domains. Then, qualitative and quantitative analyses of antiphase domains, micro-twins, and stacking faults are reported using complementarity of the local transmission electron microscopy and the statistical x-ray diffraction approaches.