All-trans-β-carotene has important functions of light collection and light protection, and it is also an important electrooptical material. The Raman spectra of polyenes are a result of the modulation effect of the π electron energy gap on the vibration of CC bonds, which associate with the external field. So it has higher theoretical significance and practical value to study the molecular structure and properties change under the external field. Ultraviolet-visible absorption spectra and resonant Raman spectra of all-trans-β-carotene in cyclohexanol were measured from 341 to 275 K. The liquid-solid phase transition of the sample appears at 295 K. The characteristic energy describes the conformational change of all-trans-β-carotene molecule. After the solution phase transition, the characteristic energy ε of all-trans-β-carotene molecule becomes bigger. And when temperature decreasing, the rate of change of the Huang-Rhys, the wavelength of UV absorption peak, electron-phonon Parameter, RSCSs of the CC bond increase. the Huang-Rhys in solid phase is an order of magnitude higher then liquid phase. The characteristic energy of liquid is 0.206 7 eV. The characteristic energy of liquid is 0.559 6 eV. The increasing of the characteristic energy ε makes the rate of increasing of the effectively conjugated length becomes bigger. The decreasing of the π electric energy gap quickens. The function of moderation from electron energy gap to all-trans-β-carotene molecule enhances. Electron-phonon Parameter increases. RSCSs of the CC bond substantially increases.