A photochemical means to convert acrylate monomer emulsions into polymer nanolatexes has been explored using radical miniemulsion photopolymerization. Our aim is to offer a complete overview through a stepwise mechanistic investigation, addressing first the key aspect of the electronic excitation of the photoinitiator in monomer miniemulsions and ending with the implementation of a photochemical reactor. In a first step, the photon flux absorbed by different photochemical initiators was investigated as a function of the miniemulsion droplet size. A series of miniemulsion polymerizations were also performed and the effects of the primary experimental parameters on the reactions kinetics, molar masses, and colloidal properties were assessed. As expected, droplet size, incident photon flux, and the nature of the photochemical initiator were found to be the primary reaction parameters. Finally, miniemulsion polymerizations were performed in an annular photochemical reactor in batch and semibatch processes.