Alkaline treatment with steel slag and NaOH addition were investigated under different pH conditions for the fermentation of waste activated sludge. Better performance was achieved in steel slag addition scenarios for both sludge hydrolysis and acidification. More solubilization of organic matters and much production of higher VFA (volatile fatty acid) in a shorter time can be achieved at pH. 10 when adjusted by steel slag. Higher enzyme activities were also observed in steel slag addition scenarios under the same pH conditions. Phosphorus concentration in the supernatant increased with fermentation time and pH in NaOH addition scenarios, while in contrast most phosphorus was released and captured by steel slag simultaneously in steel slag addition scenarios. These results suggest that steel slag can be used as a substitute for NaOH in sludge alkaline treatment.