As one of the hazardous heavy metal ion pollutants, Cr(VI) has attracted much attention in the sewage treatment research field due to its wide distribution range and serious toxicity. In this paper, cellulose fibers were prepared by wet spinning and followed by freeze drying, resulting in large porosity. Subsequently, in-depth sulfhydryl modification was applied with cellulose fibers for efficient and rapid adsorption of Cr(VI). The maximum adsorption capacity of sulfhydryl-modified cellulose fibers to Cr(VI) can reach 120.60 mg g−1, the adsorption equilibrium can be achieved within 300 s, and its adsorption rate can reach 0.319 mg g−1 s−1. The results show that the in-depth sulfhydryl-modified cellulose fibers perform excellent adsorption capacity for chromium, and are also available for other heavy metal ions. At the same time, the low cost and environmentally friendly property of the as-synthesized material also demonstrate its potential for practical usage for the treatment of heavy metal ion pollution in waste water.