The adsorption of methylene blue (MB) onto pore-expanded calcium fluoride sludge (ECF) by the batch adsorption technique was investigated. The results showed that the adsorption capacity increased with increasing MB concentration but decreased as pH was increased. In order to investigate the adsorption mechanisms, three simplified isotherm models and kinetic models were used in this study. The best-fit adsorption isotherm was achieved with the Temkin model. Furthermore, the pseudo-second-order kinetic model agreed very well with the dynamical behavior for the adsorption of MB onto ECF. Thermodynamic studies revealed that the adsorption process of MB onto ECF was spontaneous and exothermic. The results indicated that ECF adsorbed MB efficiently and could be used as a waste adsorbent for the removal of cationic dyes in wastewater treatment.