Model P-chirogenic phosphonates derived from isopinocampheol, offering an excellent experimental system for studying chirality on the phosphorus chiral center, were studied using a set of chiroptical methods including ECD, VCD and ROA. Thanks to their rigidity, limiting the number of possible conformers, we successfully correlated the experimental UV-vis/ECD, IR/VCD and Raman/ROA results with DFT calculations. This allowed us to confidently assign the absolute configuration of our models, and our assignment is consistent with X-ray diffraction (XRD) data. Furthermore, we identified phosphorus-related signals in chiroptical spectra. Specifically, the low frequency P-involving bending modes, which are only visible in ROA spectra and well-reproduced by calculations, may play a key role in determining the stereochemistry of the phosphorus chiral center. These findings lay a solid foundation for further investigation of P-chirogenic compounds, including more complex systems, using chiroptical methods, particularly ROA.