A facile photocatalytic Pickering emulsion polymerization process was developed to fabricate polymer/clay composite microcapsules. Photolatent Pickering emulsions of oil (monomer, crosslinker, Irgacure 819 and octane) in water were prepared using palygorskite fibers (PAL) as particulate emulsifier. The effect of PAL concentration on the emulsion stabilities was well studied. 3 wt% of PAL fibers were required in order to obtain a stable Pickering emulsion. Moreover, serials of factors on the formation of microcapsules have been investigated, such as PAL concentration, photoinitiator percentage, light intensity, crosslinker/monomer radio and monomer type. Under the appropriate conditions, polymer/PAL microcapsules with spherical morphology can be produced easily. Consequently, a formation mechanism of the microcapsules has been proposed.