Effective processing and use of coal slime is of great significance to protect the environment and save resources. Different coal slimes (untreated with 43 wt% ash content, crushed and flotation treated with 10 wt% ash content, and pre-carbonized) were activated with KOH to prepare porous activated carbon. The results show the activated carbon prepared from coal slime with 10 wt% ash had high specific surface area (3037 m2/ g) and pore volume (1.66 cm3/ g), which was ascribed to the suitable contents of minerals as template and oxygen-containing functional groups. Electrochemical measurements exhibited the best specific capacitance of 220 F/g at 0.1 A/g and the cycle stability of over 100% capacitance retention after 1000 cycles at 5 A/g in 6 M KOH solution. Due to the high specific surface area, superior electrochemical performance, and facile and low cost, developing highly porous activated carbon for supercapacitors is one alternative way for effective use of coal slime waste.