As a photocatalyst with good prospects, TiO2 has the shortcomings of easy agglomeration and no catalytic performance under visible light. The purpose of the present study was to help solve these problems by employing muscovite as a carrier for N-doped TiO2 in a nanocomposite. The nanocomposites were prepared by a liquid precipitation-grinding method using muscovite as the matrix and urea as the nitrogen source. The crystal structures, chemical bonding, and micromorphology of the nanocomposites were analyzed by X-ray diffraction, infrared absorption spectrometry, and field emission scanning electron microscopy, respectively. Visible and ultraviolet (UV-Vis) light absorption of the nanocomposites was analyzed by solid ultraviolet diffuse reflectance spectroscopy. The photocatalytic effect of the nanocomposites was studied based on the degradation of rhodamine B (RhB) solution. The photocatalytic degradation product of RhB was detected by high-performance liquid chromatography-mass spectrometry, revealing that N-doping inhibits the growth of TiO2 nanoparticles. The photocatalytic performance of N-TiO2/muscovite composite nanomaterials decreased with increasing heat-treatment temperature. N-doped TiO2/muscovite nanocomposites that were heated at 400°C showed the best photocatalytic performance under visible-light illumination with an RhB degradation of 97%.