Pyromellitic dianhydride-modified nanoporous magnetic cellulose–chitosan microspheres (PNMCMs) were designed and synthesized to introduce abundant carboxyl groups onto the basic microstructure. The novel microspheres were studied by scanning electron microscopy (SEM), Fourier-transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD) analysis, thermogravimetric analysis (TGA), and X-ray photoelectron spectroscopy (XPS). Subsequently, a batch technique was applied to investigate various environmental parameters that could affect the adsorption behavior of the PNMCMs. Due to its nanoporous structure and large quantity of carboxyl groups, the cellulose/chitosan-based bioadsorbent exhibited excellent adsorption performance for removal of Pb(II) ions and methylene blue (MB) from aqueous solution, with maximum adsorption capacity of 384.6 and 833.3 mg/g, respectively. Furthermore, the adsorption kinetics and isotherms of Pb(II) ions and MB on PNMCMs obeyed the pseudo-second-order and Langmuir isotherm models, and the rate of adsorption was found to be controlled by film diffusion. Finally, the PNMCMs with adsorbed Pb(II) and MB could be easily regenerated using HCl, retaining removal capacity of almost 89% after six repeated uses.