Abstract‘Doce de leite’, a dairy product widely consumed in Brazil as a dessert or cake filling, is obtained from the heat treatment of milk and sucrose. On heating, the Maillard reaction occurs with the formation of desirable brown‐coloured products with a characteristic and pleasant flavour. However, the reaction can also lead to changes in nutritive value. In order to follow chemically the extension of the Maillard reaction and its effect on the nutritive value of ‘doce de leite’ its commercial processing was followed. Increases in the level of free 5‐hydroxymethylfurfural and in absorption at 420 nm by pigments attached to the protein were observed. The amino acid analysis showed a significant decrease in lysine levels (33%) as well as in arginine (11%) and histidine (10%). There was also a reduction in available lysine levels, as measured by the fluorodinitrobenzene (50.6%) and by the 2,4,6‐trinitrobenzenesulphonic acid (23.5%) methods. These results suggest a deleterious effect of the processing of ‘doce de leite’ on the nutritive value of the milk.