The aim of the present study was to compare five reducing sugars (ribose, xylose, arabinose, glucose and fructose) with respect to their relative reactivity in the Maillard reaction (MR) (55 °C, pH 6.5) with a shrimp hydrolysate. For each system, the extent of the MR was assessed for a 24-h period by monitoring browning intensity, free amino group disappearance and sugar consumption. Results revealed the prevailing propensity of pentoses over hexoses to react in the MR, with a distinguishable behaviour for the ribose-hydrolysate system. Interestingly, pentoses were shown to mainly differ in terms of reaction rate. Complementary data on the chemical composition of the MR products (MRPs) were provided by size-exclusion chromatography, thus demonstrating the occurrence of some molecular rearrangements detected at 294 nm. The modification of protein substrates through the MR could represent a key step in the formation of new molecules and constitute a promising means to produce high value-added ingredients with biological and techno-functional properties.