Bicontinuous Pickering emulsions (bijels) are a physically interesting class of soft materials with many potential applications including catalysis, microfluidics and tissue engineering. They are created by arresting the spinodal decomposition of a partially-miscible liquid with a (jammed) layer of interfacial colloids. Porosity L (average interfacial separation) of the bijel is controlled by varying the radius (r) and volume fraction (ϕ) of the colloids (L ∝ r/ϕ). However, to optimize the bijel structure with respect to other parameters, e.g. quench rate, characterizing by L alone is insufficient. Hence, we have used confocal microscopy and X-ray CT to characterize a range of bijels in terms of local and area-averaged interfacial curvatures; we further demonstrate that bijels are bicontinuous using an image-analysis technique known as ‘region growing’. In addition, the curvatures of bijels have been monitored as a function of time, which has revealed an intriguing evolution up to 60 minutes after bijel formation, contrary to previous understanding.