Flurbiprofen (Fp), a nonsteroidal anti-inflammatory drug (NSAID) currently in use for arthritis pain relief and in clinical trials for metastatic prostate cancer, can induce photosensitization and phototoxicity upon exposure to sunlight. The mechanisms responsible for Fp phototoxicity are poorly understood and deserve investigation. In this study, the photodecarboxylation reaction of Fp, which has been assumed to underpin its photoinduced side effects, was explored by femtosecond transient absorption (fs-TA), nanosecond transient absorption (ns-TA), and nanosecond time-resolved resonance Raman (ns-TR3) spectroscopic techniques in pure acetonitrile (MeCN) solvent. Density functional theory (DFT) calculations were also performed to facilitate the assignments of transient species. The resonance Raman and DFT calculation results reveal that the neutral form of Fp was the predominant species present in MeCN. Analysis of the ultraviolet/visible absorption spectrum and results from TD-DFT calculations indicate that the second excited singlet (S-2) can be excited by 266 nm light. Due to its intrinsic instability, S-2 rapidly underwent internal conversion (IC) to decay to the lowest lying excited singlet (S-1), which was observed in the fs-TA spectra at very early delay times. Intriguingly, three distinct pathways for SI decay seem to coexist. Specifically, other than fluorescence emission back to the ground state and transformation to the lowest triplet state T-1 through intersystem crossing (ISC), the homolysis of the carbon alpha-bond decarboxylation reaction proceeded simultaneously to give rise to two radical species, one being carboxyl and another being the residual, denoted as FpR. The coexistence of the triplet Fp (T-1) and FpR species was verified by means of TR3 spectra along with ns-TA spectra. As a consequence of its apparent high reactivity, the FpR intermediate was observed to undergo oxidation under oxygen-saturated conditions to yield another radical species, denoted as FOR, which subsequently underwent intramolecular hydrogen transfer (IHT) and dehydroxylation (DHO) to form a final product, which could react with the carboxyl from the decarboxylation reaction to generate a minor final product. TD-DFT and transient state (TS) calculations for predicting the absorption bands and activation energies of the transient species produced in the photodecarboxylation reaction have provided valuable mechanistic insights for the assignment of the intermediate species observed in the time-resolved spectroscopy experiments reported here. The results of the time-resolved spectroscopy experiments and DFT calculations were used to elucidate the reaction mechanisms and intermediates involved in the photochemistry of Fp.