Spheres of silicon resins with different compositions were prepared in one-step reaction from mixtures of water and water-insoluble precursors of polysiloxanes (PSO) and polysilsesquioxanes (PSQ) using different amines as catalysts. The presence of PSO and PSQ in the spheres was confirmed by their mechanical properties and FTIR spectroscopy. Spheres of pure PSO were obtained from only dimethoxymethylvinylsiloxane (DMMVS) and 3-mercaptopropylmethyldimethoxysilan (MPMDMS) when the reaction was induced with appropriate catalysts. DMMVS and MPMDMS always gave the most promising results regarding the formation of discrete solid spheres with the minimum tendency to form monolithic solids or fluid-like, premature products. The spheres were characterized by optical microscopy, scanning electron microscopy (SEM), and Fourier transform infrared (FTIR) spectroscopy. The mixtures containing larger amounts of PSO precursors commonly gave lower yields and softer spheres.