Hybrid organic-inorganic materials were fabricated using sol-gel technique using poly(methyl methacrylate) and methacrylic acid 3-(trimethoxysilyl)propyl ester (MAMSE) with 90/10, 80/20 and 70/30 (%w/w) ratios with tetrahydrofuran (THF) solvent. The thin films were then characterized using FTIR spectra, SEM, DSC and TGA thermograms. From the preliminary characterization, the hybrid material was found to have nano and ultra scale tight pore ranges. FT-IR spectroscopy uncovered all the signature peaks characteristic of silicate structures in the near-surface regions. Fingerprints of Si-O-Si groups in cyclic and linear molecular substructures are present. The SEM image clearly shows that hybrid materials have homogenous and smooth surface. DSC analysis of the material shows interesting phenomenon regarding glass transition temperature (Tg). The hybrid material was found to have higher Tg than pure PMMA. From TGA analysis, the hybrid materials were observed to have higher thermal stability than pure PMMA.