The invention relates to an in-situ Raman light electrochemical cell by employing a TiO2NTs/Ti sheet shape electrode and an application thereof. The in-situ Raman light electrochemical cell comprises a cell body, a top cover, a pedestal, a reference electrode switch port, a counter electrode and a TiO2NTs/Ti work electrode; the in-situ Raman light electrochemical cell employs a three-electrode system, the TiO2NTs/Ti electrode is taken as the work electrode, Pt filament is the counter electrode, Ag/AgCl electrode can be taken as a reference electrode, illumination of 365 wavelength can be provided on the work electrode, certain bias voltage is applied for photoelectrocatalysis degradation, a Raman light spectra of an organic matter under different reaction time enables in-situ acquisition by employing a microscopic confocal Raman spectrometer, and a degrading mechanism of the organic matter on the TiO2NTs/Ti electrode can be obtained by analysis of the Raman light spectra. Compared with prior art, the assembling is simple, liquid addition is simple, liquid layer thickness is easily controlled, and good effect can be generated on the practical research and application aspect.