We have developed a highly time-resolved photoluminescence spectroscopy based on the excitation correlation method. Successive irradiation of a pair of ultrashort light pulses with different wavelength combinations taken from two sub-picosecond lasers has exposed both temporal and energetic correlation in photoluminescence intensity associated with a nonlinear response of a sample. An optical sampling technique has been introduced successfully in order to avoid consideration of the synchronization control of ultrashort light pulses. We have demonstrated the abilities of this technique by applying to the nonlinear photoluminescence dynamics of organic dye molecules in solution.