A microfluidic flow lithography approach was investigated to synthesize highly porous nonspherical particles and Janus particles in a one-step and high-throughput fashion. In this study, using common solvents as porogens, we were able to synthesize highly porous particles with different shapes using ultraviolet (UV) polymerization-induced phase separation in a microfluidic channel. We also studied the pore-forming process using operating parameters such as porogen type, porogen concentration, and UV intensity to tune the pore size and increase the pore size to submicron levels. By simply coflowing multiple streams in the microfluidic channel, we were able to create porous Janus particles; we showed that their anisotropic swelling/deswelling exhibit a unique optical shifting. The distinctive optical properties and the enlarged surface area of the highly porous particles can improve their performance in various applications such as optical sensors and drug loading.