The ultrafast relaxation of p-nitroaniline (PNA) in water and acetonitrile is studied experimentally and theoretically. Transient absorption spectra are measured by the pump-supercontinuum probe technique (PSCP) after 50 fs excitation at 400 nm. The relaxation includes several stages with distinct time scales: solvation, intramolecular charge transfer (CT), internal conversion and cooling. The spectral evolution before 100 fs reflects mainly solvation with dynamic Stokes shift of 3500 cm(-1) in acetonitrile and 4000 cm(-1) in water. CT and internal conversion are governed by twisting of the -NO2 group and proceed in water with 120 and 250 fs, respectively. A hot ground state upon internal conversion is characterized by an initial temperature of 1400 K. The subsequent solute-solvent energy transfer is characterized by exponential behavior between 1 and 3 ps and by a nonexponential decay at longer delays, the solute cooling time lies in the range 0.85-1.3 ps.