Hyperbranched polymers obtained by the polymerization of AB2-type monomer with a substitution effect on the B2 groups were studied by means of the kinetic model. In this polymerization with the substitution effect, if one of the B2 group reacts first, the reactivity of the remaining unreacted B group will be changed. The profiles of the degree of polymerization, polydispersity, degree of branching, and structural units of the hyperbranched polymers with the conversions were all calculated by the generating function method. It is shown that the weight-average degree of polymerization and the degree of branching of the hyperbranched polymers having substitution effect differ from that with equal reactivity of the B2 groups. If the substitution effect causes an increase in the rate constant after one of the B2 groups has reacted, a broader molecular weight distribution and a higher degree of branching are observed.