The present study introduces a facile single-source precursor preparative access to bamboo-like multiwalled carbon nanotubes (MWCNTs) highly dispersed within a mesoporous silica-rich matrix. The metal-free single-source precursor was synthesized via a one-pot sol-gel process using tetramethyl orthosilicate (TMOS) and 4,4'-dihydroxybiphenyl (DHBP) and converted subsequently via pyrolysis under an argon atmosphere into MWCNT/silica nanocomposites. The in situ segregation of the highly defective bamboo-like MWCNTs was carefully investigated and has been shown to occur within the mesopores of the silica-rich matrix at relatively low temperatures and without the use of a metal catalyst. The experimental results have been supported by extensive computational simulations, which correlate the molecular architecture of the single-source precursor with the structural features of the carbon phase segregating from the silica matrix. Furthermore, the role of hydrogen in the stability of the prepared nanocomposites as well as in the high-temperature evolution and morphology of the segregated MWCNTs has been discussed based on vibrational spectroscopy, calorimetric studies and empirical potential calculations. The results obtained within the present study may allow for designing highly-defined nanocarbon-containing composites with tailored structural features and property profiles.