The toxicity and carcinogenicity of Cr(VI) makes it a major threat to the health of animals and people. However, how to efficiently remove Cr(VI) still faces important challenges. In this study, a new metal-free polypyrrole-red phosphorus (PPy-RP) composite is successfully synthesized by in-situ oxidation polymerization for Cr(VI) removal from wastewater. The maximum adsorption capacity (qm) of Cr(VI) on PPy-RP-1 is 513.2 mg/g when the pH value is 2, which is far superior to RP nanosheets (207.8 mg/g) and PPy (294.9 mg/g). The improved qm can be ascribe to the good dispersion and increased specific surface area of PPy-RP adsorbent. Encouragingly, PPy-RP adsorbent still exhibits excellent stability after 7 cycles tests without a significant decline in removal efficiency, and remain above 81.4%. Based on the fittings of adsorption isotherms and kinetics, the process conforms to the pseudo-first-order kinetic model and the single-layer adsorption of the Langmuir model with an R2 value of 0.98533. The adsorption process is chemical and monolayer. The experimental result demonstrates that the PPy-RP can efficient removal Cr(VI) by electrostatic attraction and complexation reaction (formation of N-Cr(VI) bond) through the PPy on the surface. The results of this study indicate that PPy-RP is a promising adsorbent to remove the Cr(IV).