In this article, 316L stainless steel hollow spheres (316L HS) and polyurethane (PU) resins were used to prepare a novel metallic-hollow-sphere/polyurethane (MHSP) acoustic composite by casting. The acoustic experimental results of this composite revealed that compared to monolithic PU, the sound transmission loss of the composites increased and the maximum sound absorption peak shifted to lower frequency with the change of acoustic impedance and resonance frequency. When the surface of metallic hollow sphere used in MHSP composite was modified by silane coupling agent, the sound insulation and sound absorption performance of MHSP composites were further improved. This is related to the addition of the molecular layer of coupling agent between MHSP matrix. In addition, the addition of silane coupling agent creates PU foaming in matrix, resulting in a large number of pores and gaps that can increase the sound waves energy loss through air friction and heat exchange.