Because of either thermal/chemical instability or high optical loss in noble metal nanostructures, searching for alternative plasmonic materials is becoming more and more urgent, considering the practical biosensing applications under various extreme conditions. In this work, titanium nitride (TiN), a low-loss metal-like material with both excellent thermal and excellent chemical stabilities, was proposed to composite with Ag hollow nanosphere (HNS) nanostructures as an effective surface-enhanced Raman scattering (SERS) substrate to realize both highly sensitive and highly stable molecular detection. Because of the multiple-mode local surface plasmon resonance around the spherical composite nanospheres and the "gap effect" derived from the ultrasmall nanogaps within the precisely controlled plasmonic arrays, an intensively enhanced local field was successfully induced on this SERS substrate. Combined with the unique charge transferring process between Ag and TiN, a synergistically enhanced SERS sensitivity involving both physical and chemical mechanisms was achieved. Especially, with the isolation of TiN, a time-durable Raman detection on these TiN-Ag HNS arrays was accomplished, showing great potential for practical applications.