This work demonstrates the facilities offered by density functional theory (DFT) to calculate the molecular structural and spectral properties of tri-n-butyl phosphate (TBP) and its derivatives, namely, di-n-butyl phosphate (HDBP) and mono-n-butyl phosphate (H2MBP). The computed parameters including frontier molecular orbitals and HOMOLUMO transitions indicated the TBP has the lowermost total energy with a lager HOMOLUMO energy bandgap followed by HDBP and H2MBP. These outcomes in terms of reactivity and stability were reversed counting their dipole moments. The simulated spectra of FTIR and Raman suggested these techniques could be considered as powerful for qualitative analysis of these compounds.