The water‐insolubilization mechanism of exogenous primer dextran with 1,3‐α‐d‐glucan synthase (EC 2.4.1.‐) from Streptococcus mutans was studied. The 1,3‐α‐d‐glucan synthase solution, containing sucrose and exogenous primer dextran, was incubated briefly. Water‐insoluble glucan was synthesized. At the same time, water‐soluble glucan, mainly derived from exogenous primer dextran, decreased. Linkage analysis data of glucan produced revealed that 1,3‐α‐d‐glucoside bonds increased. Exogenous primer dextran was changed by the action of 1,3‐α‐d‐glucan synthase to water‐insoluble glucan. The results suggest that in a short‐term reaction system of outside primer‐insertion type, the 1,6‐α‐d‐glucoside bond forms the main chain of water‐insoluble glucan.