The results of a femtosecond laser investigation of the photophysical and photochemical properties of the DCM styryl laser dye molecule are reported. Femtosecond pump-probe experiments (absorption/gain spectroscopy using a white light continuum and up-conversion fluorescence spectroscopy) show a red shift of the gain and emission spectra and a blue shift of the S 1 → S N absorption band only due to a fast reorganization of the solvent cage around the highly polar fluorescent first singlet excited state of DCM. This first complete study (spontaneous emission, gain and absorption) of DCM with a pump-probe intercorrelation function around 300 fs (FWHM) demonstrates that the hypothesis of a transition from a locally excited (LE) to a twisted intramolecular charge transfer (TICT) state is not valid for DCM.