In this study, the evolution of sigma-phase development in a 2205 duplex steel was studied following thermal ageing in the temperature range 750–850 °C for periods up to 100 h. A suite of materials analysis techniques including combined electron backscatter diffraction–energy-dispersive X-ray imaging and magnetic force microscopy are used to quantify the change in volume fraction of the phases. The experimental results for each ageing condition are compared with the results from other ageing experiments and the predictions from the computer modelling. They show good correlation for the amount of sigma phase formed under a range of ageing conditions (and thus varying quantities of sigma phase). EBSD measurements showed no preferential orientation relationships relative to the parent ferrite for the nucleation of sigma phase, implying that the minimisation of boundary misorientation energy is not significant in determining sigma-phase nucleation sites. The results are discussed with respect to the experimentally measured properties of sigma phase and the kinetics of the precipitation process.