Exposure to ultraviolet (UV) light could cause photodamage to biomolecular systems and degrade optoelectronic devices. To mitigate such detrimental effects from the bottom up, we strategically select a photosensitive molecule pyranine and implement femtosecond electronic and Raman spectroscopies to elucidate its ultrafast photoprotection mechanisms in solution. Our results show that pyranine undergoes excited-state proton transfer in water, while this process is blocked in methanol regardless of excitation wavelengths (267, 400 nm). After 267 nm irradiation, the molecule relaxes from a higher lying electronic state into a lower lying singlet state with a <300 fs time constant, followed by solvation events. Transient Raman marker bands exhibit different patterns of intensity dynamics and frequency shift that elucidate the real-time interplay among conformational motions, photochemical reaction, and vibrational cooling after excitation. More energetic photons are revealed to selectively enhance certain relaxation pathways. These mechanistic findings offer new guidelines to improve the UV tolerance and stability of the engineered functional molecules in materials and life sciences.