Rationale: Carbides, including tellurium carbides (TeC), play crucial roles in diverse applications, but TeC synthesis has not been described in the literature. Laser ablation synthesis (LAS) coupled with mass spectrometry was used here for in situ TeC clusters synthesis and identification of the reaction products to better understand TeC formation. Methods: Laser desorption ionization time-of-flight mass spectrometry (LDI-TOFMS) was used to generate the TeC clusters and determine their stoichiometry via computer modeling of isotopic patterns. Results: A simple one-pot procedure was developed for Te-nanodiamond nanocomposite preparation. A suspension of fine-powdered Te was mixed with a suspension of nanodiamonds (both in acetonitrile), and the resulting precipitated nanocomposite was suitable for the synthesis of TemC(n) clusters using LDI. Various unary and binary clusters were formed. The stoichiometry of the novel TemC(n) clusters, determined via computer modeling of isotopic patterns, is reported here for the first time. Conclusions: The Te-nanodiamond composite was found to be the most suitable precursor for the generation of TemC(n) clusters. In total, 35 binary TemC(n) clusters were identified, when several of them were not obtained using commercial TeC material.