A growth mechanism of carbon nanotubes (CNTs) without any externally added catalyst is reported in this study. Instead of any externally added catalyst, the constituents of the used soda lime glass substrates seem to play the pivotal role in the growth of CNTs. XPS analysis of the synthesized CNTs reveal that among the various constituents of soda lime glass, sodium (Na) emerges as the primary catalyst for initiating CNT growth. The adopted PECVD technique involving an especially designed spiral-shaped fused hollow cathode source for generating the required atmospheric pressure plasma makes such synthesis easily feasible. The important key factors influencing CNT growth include substrate temperature and plasma pre-treatment of the substrate. Plasma pre-treatment of the substrate at an elevated temperature leads to the formation of catalyst nanoparticles on the surface of the substrate. This report features a detailed CNT growth mechanism proposed on the basis of optical emission spectroscopy and XPS analyses. To be precise, this study demonstrates a novel Na-catalysed synthetic approach for achieving uniform CNT growth on glass substrates without using any externally added catalyst, facilitating the preparation of clean CNTs.