We performed experimental and ab initio studies on tetravinylsilane cation (TVS+) and its ionic and neutral fragmentation products. The aim of the Study is the assignment of the products formed in electron impact ionization reaction of TVS. The experimental data were compared with ab initio data calculated at the MP2/cc-pVDZ level of theory. We found good agreement between the calculated reaction enthalpies and experimental appearance energies of the ions. More generally, our calculations reveal that there is a competition between intramolecular isomerization and fragmentation processes occurring after ionization of TVS. leading to the formation of a multitude of neutral and ionic species important for characterizing the silicon-carbon-containing plasma and media. New routes for the synthesis of bearing silicon molecules are suggested.