3D palygorskite (PAL)/bismuth oxychloride (BiOCl) composite microspheres were easily synthesized through a facile room temperature reaction, in which BiOCl was coupled with palygorskite (PAL) to form PAL/BiOCl nanocomposites. The employment of PAL significantly exerted great effects on the morphologies and visible-light photocatalytic performance of PAL/BiOCl nanocomposites. With gradually increasing the PAL amounts, the 3D composite microspheres were assembled with BiOCl nanosheets and palygorskite nanorods. The nanocomposites exhibited enhanced photocatalytic activities for degrading rhodamine B (RhB) under visible light irradiation, owing to its 3D hierarchical microsphere nanostructure and constructed composite with well-matched band structure and tight intercontact.