The invention discloses an optical frequency domain reflectometer with optical wave frequency shift modulation, which comprises a narrow linewidth scanning laser, a first optical fiber coupler, an optical circulator, a to-be-measured optical fiber, an optical wave frequency shifter, a second optical fiber coupler, a first polarization beam splitter, a second polarization beam splitter, a first balanced photodetector, a second balanced photodetector, a third optical fiber coupler, a first Faraday rotating mirror, a second Faraday rotating mirror, a reference optical fiber interferometer, a photodetector and a signal acquisition and processing unit. Through frequency shift modulation on measurement light and reference light, interference signals produced by superposition of scattering signal light of the to-be-measured optical fiber which is symmetrical about zero delay and local oscillation light are separated on the spectrum. According to the optical frequency domain reflectometer with optical wave frequency shift modulation, mutual interference among the interference signals of the to-be-measured optical fiber scattering signal light which is symmetrical about zero delay can be suppressed, measurement of the scattering signal light which is symmetrical about zero delay can be realized, and the maximum optical fiber measurement length can be improved.