TEMPO-media oxidation and laccase have been successfully used in fiber degumming, but the combination of the two methods in the hemp degumming process has not yet been reported. In this paper, an alternative and efficient way for the pretreatment of hemp degumming was proposed as a combination of TEMPO-media oxidation with laccase and was a TEMPO-laccase system. A chemical composition analysis, Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), and scanning electron microscopy (SEM) were applied to systematically analyze and compare the degumming efficiency between the TEMPO-laccase system and other pretreatments. The results showed that after the TEMPO-laccase system degumming process, a clean and smooth surface of the degummed fibers could be observed and the non-cellulosic materials were greatly removed without any crystalline transformation. The hemp fibers after the TEMPO-laccase system degumming process had the most desirable linear density of 6.64 dtex and a tenacity value of 3.41 cN/dtex. This new pretreatment had a considerable effect on hemp degumming, which holds promise for use of high-value textiles.