The feasibility of on-site generated chlorine (OSG chlorine) as an alternative disinfectant to chlorine gas was evaluated in terms of total organic carbon (TOC) removal, disinfection efficiency, biofilm control, disinfection by-products (DBPs) formation, chlorine decay rate, and volatility. Chlorine gas decreased the pH of the treated water by -0.1 per mg/L of free available chlorine (FAC) while OSG chlorine increased the pH by + 0.06 per mg/L. OSG chlorine with more hypochlorite ion (OCl-) at higher pH was less effective in the inactivation of suspended bacteria and TOC removal but remained in the distribution system longer and controlled biofilm formation more effectively than chlorine gas. The DBPs formation by OSG chlorine was not significantly different from that by chlorine gas except for the reduction of Haloacetonitriles. Hypochlorous acid (HOCl) was more volatile than OCl-, indicating the lower volatility of FAC in the OSG chlorine-treated water. Two types of OSG systems, “Mixed oxidants” and OSG hypochlorite, did not show any significant difference in disinfection, DBPs formation, and chlorine decay rate (paired t-test, p = 0.40, 0.11 ~ 0.70, > 0.42). A significant synergy effect by oxidants other than FAC cannot be expected in the use of “mixed oxidants” at a water treatment plant.