<p>Commercially available and inexpensive potassium carbonate (K₂CO₃) has been applied to the hydrothiolation of mercaptopropylisobutyl POSS (<b>SQ-SH</b>) with α,β-unsaturated carbonyl compounds of different types. This innovative approach has been proved to be effective for a wide range of substrates, leading to novel classes of functionalized SQ-based materials in yields exceeding 90% under ambient temperature, air and transition metal-free conditions. Additionally, the proposed synthetic strategy has been used for the modification of chalcones, the compounds with significant medicinal and synthetic potential. As a result, twelve new mercapto-modified nanomaterials containing carbonyl groups were obtained and comprehensively characterized by spectroscopic methods and mass analysis. The selected product of great practical application was studied in terms of its thermal properties.</p>