Transition-metal-catalysed carbocyclisation reactions serve as powerful synthetic methods for the construction of various types of ring systems. In particular rhodium promoted silylformylation of functionalised alkynes performed in the presence of a base directly affords polyfunctionalised β-lactones and β-lactams. Both homogeneous and supported rhodium catalysts showed good catalytic efficiencies in the silylcarbocyclisation process. Nanoclusters of rhodium, generated by means of the metal vapour synthesis techniques and deposited on various matrices, resulted extremely reactive due to the very small dimensions of the metal particles.