The dynamics of photochemical hydrogen-atom abstraction in ethyl 4-formyl-1,3-dimethylpyrazole-5-carboxylate (EFDPC) has been studied by femtosecond through microsecond time-resolved absorption techniques in different solvents at room temperature. The photoreaction initiates within the time period of the excited singlet state (S-1) lifetime and gives transient photoproduct with lambda(max) similar to 580 nm. The transient absorption spectra are consistent with that obtained in the steady state after the photolysis of EFDPC at cryogenic temperature in various glassy matrixes, as well as in a solid sate. The photoproduct was a non-Kekule molecule of zwitterionic form resulting from gamma-hydrogen abstraction by an excited formyl group followed by a very short-lived intermediate singlet 1,4-biradical, which is identical to that of tetramethyleneethane (TME) biradical. The photoproduct exists for a few microseconds in solution before the reverse reaction occurs to come back to the original compound. The density functional theory (DFT) calculations have also been made to elucidate the energetics along the reaction pathway, the geometrical conformation of the intermediate, and the final photoproduct.