Recently, a type of synthetic highly efficient OLED molecule based on a hybridized local excitation and charge transfer (HLCT) character has received much attention as a potential high-efficiency fluorescent OLED material. In this article, we report the relaxation dynamics of the excited states of cyano-substituted oligo α-phenylenevinylene-1,4-bis(R-cyano-4-diphenylaminostyryl)-2,5-diphenylbenzene (CNDPASDB) with HLCT character using steady-state and time-resolved spectroscopy as well as quantum chemical calculations. The dramatic dependence of the fluorescence quantum yield, radiative and non-radiative rate, as well as the excited state relaxation pathways on solvent polarity reveals that the solvation process controls the energy levels of two closely spaced electronic excited states. By employing femtosecond transient absorption spectra, the gradual transition from the LE state to the intramolecular CT state with an increase in solvent polarity is clearly resolved. In low-polarity solvents the fluorescence of CNDPASDB is mainly emission from the LE state, whereas in high-polarity solvents non-radiative decay from the CT state dominates. And in medium-polarity solvents, because of the relatively weaker solvation-induced stabilization of the CT state, its energy could be equal to or slightly lower than that of the LE state, leading to a smaller driving force for LE → CT interconversion; therefore complete LE → CT interconversion cannot take place. In this situation, LE ↔ CT intercrossed equilibration is established and the equilibrium constant is further estimated to be about 4 according to the obtained kinetics, and the equilibrium population of the CT state is about 80%. DFT/TDDFT analysis also confirmed an efficient intercrossing of LE and CT states with an increase in solvent polarity. It is found that upon increasing the solvent polarity, the hole and electron on a molecule are entirely separated, suggesting a complete CT character. These results provide guidance for understanding the relationship between solvent polarity and the HLCT process, as well as for designing and synthesizing advanced OLED materials.