The accumulation of reducing sugars, sucrose and hexose phosphates in cv. Bintje and genotype KW77-2916 during storage at 2, 4, or 8°C was studied in relation to several catalytic activities. Bintje tubers accumulated sugars during storage at 2 or 4°C, whereas KW77-2916 showed reduced cold-sweetening at 2°C. The increase in glucose 6-phosphate and sucrose occurred concurrently and preceded the increase in reducing sugar concentration. Phosphorylase activity showed a strong interaction with temperature, storage duration and sugar accumulation in both genotypes. Invertase activity increased in Bintje concomitantly with the increase in reducing sugars, but this effect was less obvious in KW77-2916. The activities of other glycolytic and Krebs cycle enzymes showed no obvious correlation with sugar accumulation. It is suggested that the increase in phosphorylase activity acts as a triggering event in the sweetening of potato tubers during cold storage.