In this study, benzocyclobutene-functionalized organic-inorganic hybrid spherical silicon nanoparticles (BCBNPs) with controllable size (200-600 nm) and good dispersion were synthesized by a one-step sol-gel method in aqueous solution. The effect of the reaction conditions (time, precursor concentration, pH value and temperature) on the particle size of the BCBNPs and the formation mechanism of the BCBNPs were studied. What is more, homogeneously dispersed BCBNPs/divinyltetramethyldisiloxane-bis(benzocyclobutene) (BCBNPs/PDVSBCB) nanocomposites were prepared and the influence of the incorporation of BCBNPs on the properties of the nanocomposites was investigated. The dielectric constants of the BCBNPs/PDVSBCB nanocomposites were drastically reduced relative to neat PDVSBCB, and were as low as 2.25 (30 MHz). Besides, the thermal and mechanical properties of the BCBNPs/PDVSBCB nanocomposites were significantly improved, evidencing their potential applications in the field of high-performance dielectric materials.