Fermi resonance phenomenon exists in simple compounds and it also widely exists in vibration spectra of complex.The complex can be formed by adding up simple compounds.As a result,the characteristic parameters of some parts of molecule will make changes,and the molecular spectra have a significant change along with it.Benzoquinone and proline in the solution form charge-transfer complex under certain conditions,but the spectra intensity is weak,our research uses Teflon liquid-core optical fiber technology to gain high quality resonance Raman spectra.We acquire Raman spectra of Benzoquinone and its complex in experiments,and analyze the characteristic parameters of Fermi resonance according to J.F.Bertran quantum theory.The results shows that,because of the formation of complex,Fermi resonance peak of CO bond shifts to high wavelength,the spectra intensity decreases,the frequency space increases,the coupling coefficient increases.The explanation is that,in the solution of complex,proline is donor,while benzoquinone is acceptor,the non-bonding electron of N atom which is belong to proline transfers to the π anti-bonding orbital of benzoquinone,then n—π* charge transfer complex is produced.That causes the change of molecular energy level,changes the Raman spectra.All these researches provide new idea and clue for spectral line certification and attribution of complex molecules,complexes and polymer.