AbstractPolydimethyl siloxane combs projecting from a novolac stem were synthesized using click reaction of azide‐terminated polydimethylsiloxane (AZ‐PDMS), and novolac propargyl ether (NPE) under ambient (30°C) conditions. Dynamic mechanical analyses (DMA) indicated the transition of soft segments at nearly −100°C and that of the hard segments in the range of 25°C‐30°C. The hybrid novolac‐siloxane networks have been found to possess an elongation at break of 100%–260%. Thermal degradation behavior of the networks of different crosslink densities was studied using TGA and pyrolysis GC‐MS. Thermogravimetry revealed an anaerobic char residue of 23%–40% at 900°C. Further rise in temperature up to 1500°C has been observed to result in hardly 1% reduction in the char yield/ceramic residue, thus attributing to the presence of high char‐yielding aromatic part. The ceramic residue obtained at 1500°C under argon atmosphere was analyzed using FTIR, Raman, and XRD. XRD studies implied formation of βSiC, and SiO2. Morphology of the ceramics conformed to nanowires with diameters in the range of 20‐100 nm. The nanowire consisted of mainly SiOC as attested by EDS analysis.