The surface coating technologies without using toxic organic solvent have been highly desired to reduce VOCs emissions and operation cost as well. In the first chapter, a series of ladder-like poly (silsesquioxanes) (LPSQs) with alkyl and methacrylate functional group were strategically designed, and synthesized as a potential solvent-less coating material. Obtained LPSQs were characterized using 1H NMR and 29Si NMR, FT-IR and GPC. The LPSQs with the flexible longer alkyl side chain showed excellent fluidity (LOMASQ64, LDMASQ64). Their films were then prepared by doctor blade method without solvent and then cured by UV irradiation. Obtained transparent films showed high thermal stability and mechanical strengths such as hardness and modulus, which was much higher than the film prepared with commercial available coating solution such as AR-710F and UR-7750. In the second chapter, the fluorine functionalized LPSQs consisting of fluoroalkyl and methacrylate groups were synthesized as a solvent-free functional coating materials. Using the same strategy as described in the previous experiment, a series of the fluorine functionalized LPSQs with different lengths of the fluoroalkyl groups. Interestingly, obtained fluorine-functionalized LPSQs showed a different behaviors of viscosity in comparison to the alkyl-functionalized LPSQ, thus the LPSQs with longer fluoroalkyl groups was much viscose. This is probably due to high dipole-dipole moment of C-F bond in the fluoroalkyl chains, of which number increased to give more strong intermolecular interactions to increase viscosity. Due to C-F bond, the obtained films after UV curing gave higher thermal stability, hardness, and modulus in comparison to the corresponding alkyl functionalized LPSQs.