As an important technique to study the linear polyene molecules, Resonance Raman spectroscopy perfectly characterizes the CC vibrations modulated by the π-electron band gap. This modulation generated by electron-phonon coupling is significantly influenced by external fields. In this paper, we illustrate the dependence of CC vibration modulated by π-electron in different environments such as temperature, pressure, phase and solvent. The results show that the decrease of system energy and the narrowing of π-electron band gap lead to enhancements of the vibrational modulation. Thus, there are enhances of electron-phonon coupling as well as Raman intensity, result of which the spectra red shift. This research is of great significance for a better interpretation on the structural dependence of linear polyene's spectral properties and physical process of its resonance Raman scattering. The results also serve as an important reference for developing high quality photoelectric devices.