The stepwise photoinduced charge transfer in a series of N-carbazolyl benzoate ester push–pull chromophores has been studied in solution. Dual emission from the locally excited (LE, the lowest-energy singlet excited state of ¹L_b nature localized on the carbazole donor) and the highly polarized, intramolecular charge-transfer states of (pre)-twisted type (TICT states) is observed in non-polar and polar solvents. Ultrafast transient spectroscopy reveals that the excitation into the ¹L_b LE state is followed by rapid (∼ps) charge separation into an emissive TICT state. Excitation into the second singlet excited state localized on the carbazole (S₂) with ¹L_a nature results in sub-100 fs population of both ¹L_b and TICT states.