In recent years, the elimination of heavy metals from wastewater has become an important topic due to rapid industrialization, and it is of considerable interest to develop renewable and degradable materials for this purpose. In this work, a novel Prussian blue/polyaniline@cotton fibers (PB/PANI@CFs) composite was fabricated by a two-step process. Phytic acid doped PANI as a binding coating greatly promoted both the growth of PB and the adsorption of Cu2+. The deposition ratio of PB was as high as 24.68%. Scanning electron microscopy (SEM) displayed that PB nanoparticles were grown more uniformly in the composite and formed a perfect nanocube structure compared with PB@CFs. The successful deposition of both PB and PANI on CFs was demonstrated by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FITR), and X-ray photoelectron spectroscopy (XPS). The effect of adsorption time, adsorbent dose, initial pH value, and initial copper sulphate concentration on the adsorption of PB/PANI@CFs composite for Cu2+ was studied by static adsorption and was compared with those of PANI@CFs and PB@CFs. The results showed that the maximum removal efficiency of Cu2+ by PB/PANI@CFs can reach 93.4% within 5 h, and the maximum adsorption capacity of Cu2+ can reach 31.93 mg·g−1. The adsorption of Cu2+ on PB/PANI@CFs followed the pseudo-second order kinetic model and conformed to the Freundlich adsorption isothermal model. The PB-functionalized CFs provided new insights into the design of efficient and low-cost absorbents for heavy metal remediation. The proposed process solves two problems simultaneously, i.e., the utilization of environmentally friendly and biodegradable biomass resources and the adsorption of heavy metal ions, and is a good approach to achieve high-quality and sustainable development.