Aerobic floc-like sludge was formed in a batch reactor and the effect of cations on the formation of aerobic floc-like sludge was studied. In order to enhance the formation (rate) of aerobic floc-like sludge, cations such as $K^+$, $Na^+$, $Ca^{2+}$, and $Mg^{2+}$ were added to the seed sludge. It was found that $Ca^{2+}$ had positive effect on the formation of floc-like sludge, as measured by sludge volume index (SVI) for settle ability. The formation of floc-like sludge was confirmed by the microscopic observation after DAPI staining. The scattered forms of sludge samples at the initial stage became aggregated to form floes after $Ca^{2+}$ addition. To ensure the functions of sludge floes in a treatment plant, the gradient of ionic species around the surfaces of floc-like sludge was monitored by ion selective microelectrodes for ${NH_4}^+,;{NO_3}^-$, and pH. The effective concentration of $Ca^{2+}$ ion to form floc-like sludge was determined to be 750 mg/L (0.15 mg $Ca^{2+}/mg$ MLSS). Under the effective $Ca^{2+}$ condition, the SVI value was the lowest and large distribution of nitrifying bacteria at the outer surface was observed in the aerobic floc-like sludge. From the results, it was found that the calcium ion functioned as an agent for the formation of aerobic floc-like sludge, resulting in the enhanced nitrification.