Phenolic resin/silica hybrid ceramers were prepared through sol-gel technology. Differential scanning calorimetry and thermogravimetric analysis methods were utilized to study the thermal properties of the fabricated hybrid ceramers. The results showed that the heat resistance of the ceramers was slightly higher than that of the phenolic resin. The hydrogen bonding occurring inside the hybrid ceramers was investigated by Fourier transform infrared. The results showed that the intermolecular hydrogen bonding between the phenolic resin and the silica was stronger than the intramolecular hydrogen bonding between the phenolic resin molecules themselves. Furthermore, the hybrid ceramers were utilized to fabricate carbon-fiber-reinforced composites. The fabricated ceramer composites possessed better flexural strength and flexural modulus than that fabricated from neat phenolic resin.