The thermal degradation of ascorbic acid (AA) in orange juice was analysed over in a 20–45 °C temperature range. Dehydroascorbic acid (DA), pH and browning were also monitored. Small amounts of AA degradation could be described by first order kinetics, but when only low amounts of AA were retained sigmoidal kinetics were clearly appropriate. The Weibull model was used to describe this pattern (R2adj > 0.995). The rate constant increased with temperature according to an Arrhenius-type relationship. The activation energy was 38.6 kJ/mol and at the average temperature of the range tested, 32.5 °C, the rate constant was 64.4 × 10−3 h−1. The shape constant decreased linearly with temperature, from 2.17 to 1.13. Before the time when the maximum degradation rate occurred, pH, DA concentration and browning remained fairly constant, and then increased. It was found that this behaviour, as well as the dependence of the shape constant on temperature, might be explained by (i) the reconversion of DA into AA, following first order kinetics in relation to DA and second order kinetics in relation to AA, and by (ii) different sensitivities of the reaction rate constants to temperature. Browning was also well described by the Weibull model with a temperature independent shape constant.