Porous polymeric microspheres are among the most effective adsorbents. They can be synthesized from numerous monomers using different kinds of polymerization techniques with a broad selection of synthesis factors. The main goal of this study was to prepare copolymeric microspheres and establish the relationship between copolymerization parameters and the porosity and thermal stability of the newly synthesized materials. Porous microspheres were obtained via heterogenous radical copolymerization using 3-(trimethoxysilyl)propyl methacrylate (TMPSM) as functional monomers and trimethylolpropane trimethacrylate (TRIM) as the crosslinker. In the course of the copolymerization, toluene or chlorobenzene was used as the pore-forming diluent. Consequently, highly porous microspheres were produced. Their specific surface area was established by a nitrogen adsorption/desorption method and it was in the range of 382 m2/g to 457 m2/g for toluene and 357–500 m2/g in the case of chlorobenzene. The thermal degradation process was monitored by thermogravimetry and differential scanning calorimetry methods in inert and oxidative conditions. The copolymers were stable up to 269–283 °C in a helium atmosphere, whereas in synthetic air the range was 266–298 °C, as determined by the temperature of 5% mass loss. Thermal stability of the investigated copolymers increased along with an increasing TMPSM amount in the copolymerization mixture. In addition, the poly(TMSPM-co-TRIM) copolymers were effectively used as the stationary phase in GC analyses.