Carotenoids are a class of natural pigments that play a fundamental role in photosynthesis and optoelectronics. However, the complexity of their energy level structure and electronic states has prevented a clear interpretation of their photophysics and photochemistry. The mediating nonradiative decay of the bright S2 state to the dark S1 state of carotenoids involves a population of bridging intermediate state. Herein, time-dependent DFT was used to study the energy level and electronic excitation process of β-carotene. A π-π* transition and π electron delocalization of electron excitation could be inferred based on the difference in the electron cloud distribution of the HOMO and LUMO orbitals. Through the electronic transition contribution in the UV-vis spectra and the electron density difference between the ground state and the excited state, the electronic energy level structure and possible dark state were analyzed. On this basis, the electronic excitation process of β-carotene was theoretically studied by combining electron-hole analysis and transition density matrix (TDM). There was a charge transfer from the β-ionone ring to the long-chain in the (S0) → (S2), (S0) → (S4) and (S0) → (S5).