In order to develop high-performance adsorbents to remove toxic methylene blue (MB) from wastewater, palygorskite (Plg) was utilized as a template to prepare palygorskite/carbon (Plg/C) composites by using a hydrothermal reaction in the presence of glucose. The porous Plg/C composites were then activated with ZnCl2. The effects of the dose of the activator and the activation temperature on the crystal structure, micro-morphology, specific surface area, and adsorption performance of the porous Plg/C composites were studied systematically here. X-ray diffraction (XRD) and scanning electron microscopy (SEM) results indicated that the crystal structure of Plg was destroyed during the activation process and irregular porous carbon was closely attached to the residual aluminosilicate skeleton. The activation was optimized at 400°C with a ZnCl2:Plg/C impregnation ratio of 2:1. The sample had a specific surface area of 1497.88 m2/g, together with a total pore volume and micropore volume of 1.0355 and 0.5464 cm3/g, respectively. The MB adsorption capacity was 381.04 mg/g. Such inexpensive, high-performance, porous Plg/C composites could find potential applications in wastewater treatment.