Polydimethylsiloxane (PDMS) microspheres are prepared by mixing homogeneous dispersions of vinyl-functional PDMS and a curing agent using mechanical stirring in a series of aqueous solutions, and curing at 80 degrees C for 2h. In order to verify the experimental diameter and size distributions of the PDMS microspheres, the Hinze-Kolmogorov theory is applied to predict the mean diameter, and a population balance model as well as the maximum entropy formalism are used to describe the size distribution. Close agreement is found between experimental and theoretical results. Furthermore, vinyl functional PDMS microspheres were coated with poly(methyl methacrylate) (PMMA) by spin coating with different concentrations of PMMA solutions. The quality of the resulting PMMA shell is investigated using rheological measurements at 50 degrees C with a time-sweep procedure. The results strongly suggest that PMMA-coated PDMS microspheres react around 20 times slower than the uncoated ones, and that the PMMA shell significantly hinders the reaction between the PDMS microsphere and cross-linker. Thus the thin PMMA shells are very efficient in protecting the reactive PDMS microspheres, since the PMMA shell forms an impermeable barrier up to 50 degrees C.