The use of gold nanoparticles coated with an organic monolayer of thiol for application in chemiresistive sensors was initiated in the late 1990s; since then, such types of sensors have been widely pursued due to their high sensitivities and reversible responses to volatile organic compounds (VOCs). However, a major issue for chemical sensors based on thiol-capped gold nanoparticles is their poor long-term stability as a result of slow degradation of the monothiol-to-gold bonds. We have devised a strategy to overcome this limitation by synthesizing a more robust system using Au nanoparticles capped by trithiol ligands. Compared to its monothiol counterpart, the new system is significantly more stable and also shows improved sensitivity towards different types of polar or non-polar VOCs. Thus, the trithiol-Au nanosensor shows great promise for use in real world applications.