Often an intramolecular relaxation process takes place in a time scale similar to that of the solvent relaxation process. Under these circumstances the dynamic Stokes' shift of the probe can be modulated by the combined effect of these two relaxation processes. In the present article we have studied ultrafast solvent relaxation using three different coumarin dyes and proposed a methodology for the quantitative separation of the dynamics of two competing processes, namely, solvent relaxation and bond twisting, that take place simultaneously in the present systems.