The Maillard reaction is one of the most important phenomena occurring spontaneously during food processing and storage. However, research on the effects of Maillard reaction products (MRPs) on starch hydrolysis remains insufficient. To investigate the effects of MRPs on in vitro starch digestibility, the characteristics of glucose–glycine model system containing MRPs and digestive enzyme activities by MRPs were measured. MRPs were prepared by heating of glucose–glycine mixture solution at 90°C for different times (0, 1, 3, 9, 18, 24, and 48 h). As the Maillard reaction proceeded, browning intensity, and furosine and hydroxymethylfurfural content increased, whereas pH value decreased. The reducing power of MRPs was increased as the Maillard reaction progressed, and MRPs produced in 18 and 24 h showed the highest values (both 1.2). In MRPs heated for 48 h, the reducing sugar content and hydrolysis index were lowest values (88.6 and 87.0%) among the samples. The activity of digestive enzymes significantly decreased by adding of MRPs, as the browning of added MRPs increased. Therefore, MRPs seem to be contributed to decrease in starch digestibility, as shown by an enzymatic digestion result.