In this paper, the extraction process of flavonoids from hemp fibers was studied. Response surface methodology (RSM) analysis of the extraction parameters indicated that optimized results would be ethanol concentration 76 vol.%, bath ratio 1:50, and reaction time 139 min; therefore, an optimal extraction rate of flavonoids of 0.2275% can be obtained. The chemical structure, surface morphology and element composition of flavonoid extracts were analyzed. The test results indicated that hemp extract contains flavonoids, which can be used to extract flavonoids from hemp fiber, so as to comprehensively develop hemp fiber and reduce the discharge of waste liquid in the traditional degumming process.