Picosecond and nanosecond time-resolved resonance Raman spectroscopy combined with density functional theory calculations have been performed to characterize the structure, dynamics, and hydrogen-bonding effects on the triplet state of the phototrigger model compound p-methoxyacetophenone (MAP) in cyclohexane, MeCN, and 50% H2O/50% MeCN (v:v) mixed solvent. Analogous work has also been done to study the corresponding ground state properties. The ground and triplet states of MAP were both found to be associated strongly with the water solvent molecules in the 50% H2O/50% MeCN solvent system. A hydrogen-bond complex model involving one or two water molecules bonded with the oxygen atoms of the MAP carbonyl and methoxy moieties has been employed to explore the hydrogen-bond interactions and their influence on the geometric and electronic properties for the ground and triplet states of MAP. Among the various hydrogen-bond configurations examined, the carbonyl hydrogen-bond configuration involving one water molecule was calculated to lead to the most stable hydrogen-bond complex for both the ground and the triplet states with the strength of the hydrogen-bond interaction being stronger in the triplet state than the ground state. The increased carbonyl located hydrogen-bond strength in the triplet state results in substantial modification of both the electronic and the structural conformation so that the triplet of the hydrogen-bond complex can be considered as a distinct species from the free MAP triplet state. This provides a framework to interpret the differences observed in the TR3 spectral and triplet lifetime obtained in the neat MeCN solvent (attributed to the free MAP triplet state) and the 50% H2O/50% MeCN solvent (due to the triplet of the hydrogen-bond complex). Temporal evolution at early picosecond times indicates rapid ISC conversion, and subsequent relaxation of the excess energy of the initially formed energetic triplets occurs for both the free MAP and the hydrogen-bond complex. The triplet of the carbonyl hydrogen-bond complex appears to be generated directly from the corresponding ground state complex and it does not dissociate back to the free triplet state within the triplet state lifetime. We briefly discuss the influence of the carbonyl hydrogen-bond effect on the pi pi* triplet reactivity for MAP and closely related compounds.