The use of sustainable raw materials is now a necessity in all industries, including the production of porous microparticles. Cyrene™ is a cellulose-derived compound that is readily prepared through the reduction of the α,β-unsaturation of levoglucosenone (LGO)—a wood-based platform molecule. In this work, the importance of Cyrene™ as a potential bio-based molecule to produce sustainable porous microparticles is demonstrated. First, a methacrylic derivative of Cyrene™ (m-Cyrene) was synthesized. A microfluidic co-flow device was then established to produce m-Cyrene-based oil-in-water (O/W) controlled-size emulsions and to polymerize them by ultraviolet (UV) radiation in a vial. The continuous phase was a sodium dodecyl sulfate aqueous solution, and the dispersed phase was a mixture of m-Cyrene with methacrylic anhydride (MAN) at two different mass concentrations (i.e., 1 wt.% MAN and 92 wt.% MAN) and 2,2-dimethoxy-2-phenylacetophenone (DMPA) as a photoinitiator. The process used the lowest possible quantity of raw materials and avoided excessive purifications to produce homogeneous porous m-Cyrene-MAN microparticles. The controlled size and homogeneous size distribution of the produced polymer microparticles were confirmed by scanning electron microscope (SEM) images. The 3D microstructure as well as the porosity were determined using X-ray microtomography. The high-resolution 3D images produced indicate that the pores of the microparticles are homogeneous and that their porosity is controllable through the concentration of MAN in the monomer mixture (porosity of 30% for a 1 wt.% MAN ratio and 2% for a 92 wt.% MAN ratio). Such porosity control is very important for future potential encapsulation processes that require precise release control.