Polystyrene (PS)/silicate composites were prepared with the addition of two organoclays (orgMMT and orgZenith) and two mesoporous silicas (SBA-15 and MCF) via (i) solution casting and (ii) melt compounding methods. X-ray diffraction (XRD) analysis evidenced an intercalated structure for PS/organoclay nanocomposites. Thermogravimetric analysis indicated improvement in the thermal stability of PS-nanocomposites compared to the pristine polymer. This enhancement was more prevalent for the nanocomposites prepared with a lab-made organoclay (orgZenith). Tensile measurement results indicated that elastic modulus increment was more prevalent (up to 50%) for microcomposites prepared using mesoporous silicas as filler. Organoclay addition led to a decrease in oxygen transmission rate (OTR) values. This decrement reached up to 50% for high organoclay content films in comparison to pristine PS film. Decrement above 80% was measured for microcomposites with mesoporous silicas and 5 wt% filler content obtained via melt compounding.