In the present study, hybrid organic–inorganic composites were fabricated from epoxy–TEOS (tetraethyl orthosilicate, Si(OC2H5)4) with various ratios (0–10 wt%) of multiwall carbon nanotubes (MWCNTs) as reinforcing nanofillers by the sol–gel method. The effect of the MWCNTs ratios on the structural, optical and mechanical characteristics and the thermal conductivity of the epoxy–TEOS/MWCNTs composites is investigated. The X-ray diffraction (XRD) analysis reveals that the pure epoxy-TEOS is amorphous, while epoxy–TEOS/MWCNTs composites are crystalline with an orthorhombic crystal structure that has an average crystallite size of 3.9 ± 0.15 nm. In addition, thermal stability and thermal conductivity were improved by adding TEOS and MWCNTs, whereas the exothermic peak temperature decreases compared with pure epoxy-TEOS. Similarly, the hardness Shore-D and tensile strength reach the optimum value at 4 wt% MWCNTs content. The significant improvement in the mechanical and thermal properties of the prepared composites could be attributed to the synergistic effect of MWCNTs and epoxy–TEOS which was emphasized by Fourier transform infrared (FTIR) spectroscopy. Moreover, epoxy-TEOS sample has high optical transmittance (T) within the visible region, but the composites samples are transparent at λ < 800 nm and have a lower value of T. The indirect optical band gap decreases from 3.59 to 2.91 eV with an increase in MWCNTs fractions from 0 to 10 wt%, respectively. However, the glass transition reflects the onset of decomposition temperatures was also considerably increased. The acquired outcomes such as a large increase in thermal conductivity and tensile stress coupled with reduced T make the composites readily applicable for a variety of applications.