Titania–silica (TiO₂–SiO₂) Janus particles with high photocatalytic activity were synthesized using a Pickering emulsion method. The Janus particles were calcined at two temperatures and the effect of the calcination temperature on photocatalysis was explored. Their morphology and structure were characterized. The photocatalytic activity of the calcined Janus particles was compared with that of calcined SiO₂–TiO₂ core–shell particles and commercially available P25 TiO₂ nanoparticles. Janus particles calcined at 450 °C (Janus@450) showed significantly higher adsorption (by almost 2–14×) and rate of degradation (by almost 6.6–211×) of a photo-stable Solophenyl green dye compared to other TiO₂ structures. The higher activity of Janus@450 was attributed to its unique electronic structure which showed a significantly higher average carrier lifetime of 1.98 ns compared to 0.18 ns of other structures.