We report on mass spectrometry of residual gases after dissociation of tetramethylsilane (TMS) during the synthesis of silicon carbide (SiC) nanocrystals (NCs) by an atmospheric pressure microplasma. We use these results to provide details that can contribute to the understanding of the formation mechanisms of NCs. Mass spectrometry reveals the presence of high‐mass polymerization products supporting the key role of neutral fragments and limited atomization. On this basis, we found that the loss of methyl groups from TMS, together with hydrogen abstraction, represents important paths leading to nucleation and growth. The combination of TMS concentration and NC residence time controls the NC mean size and the corresponding distributions. For higher precursor concentrations, the reaction kinetics is sufficiently fast to promote coalescence.