Pico- and nanosecond time-resolved resonance Raman (TR3) spectroscopy have been utilized to study the dynamics and structure of p-hydroxyacetophenone (HA) and the p-hydroxyphenacyl-caged phototrigger compound p-hydroxyphenacyl diethyl phosphate (HPDP) in acetonitrile solution. Transient intermediates were detected and attributed to the triplet states of HA and HPDP. Nanosecond-TR3 measurements were done for two isotopically substituted HA molecules to help better assign the triplet state carbonyl C=O stretching and the ring related vibrational modes. The dynamics of formation and the spectral characteristics for the triplet states were found to be similar for the HA and HPDP. The temporal evolution at very early picosecond time scale indicates there is rapid intersystem crossing (ISC) conversion and subsequent relaxation of the excess energy of the initially produced energetic triplet state. B3LYP/6-311G** density functional theory (DFT) calculations were done to determine the structures and vibrational frequencies for both the triplet and ground states of HA and HPDP. The calculated spectra reproduce the experimental spectra and the observed isotopic shifts reasonably well and were used to make tentative assignments to all the experimentally observed features. The triplet states were found to have extensive conjugated pipi* nature with a single-bond-like carbonyl CO bond. We briefly compare the triplet structure and formation dynamics of HA and HPDP as well as the conformational changes upon going from the ground state to the triplet state. We discuss our present results in relation to the initial pathway for the p-hydroxyphenacyl photodeprotection process. We also compare and discuss the properties of the HA pipi* triplet state relative to the published results of other aromatic carbonyl compounds.