The polymer-ceramic hybrid, known as 'ceramer', was synthesized by a sol-gel process by incorporating different amount of alkoxide as source of silicon in resorcinol-formaldehyde in presence of basic catalyst to get different percentage of silicon in ultimate carbonized composites. FTIR of the ceramer confirms that it is a network of Si-O-Si, Si-O-CH2 and Si-OH type groups linked with benzene ring. Different amount of silicon in the ceramer exhibits varying temperature of thermal stability and lower coefficient of thermal expansion as compared to pure resorcinol-formaldehyde resin. The lower value of CTE in ceramer is due to existence of silica and resorcinol -formaldehyde in co-continuous phase. Unidirectional composites prepared with ceramer matrix and high-strength carbon fibers show lower value of flexural strength at polymer stage as compared to those prepared with resorcinol-formaldehyde resin. However, after heat treatment to 1450℃, the ceramer matrix composites show large improvement in the mechanical properties, i.e. with 7% silicon in the ceramer, the flexural strength is enhanced by 100% and flexural modulus value by 40% as compared to that of pure resorcinol-formaldehyde resin matrix composites.