We achieved external activation of local hot-spot sites in supracolloidal assembly structures. The concept was demonstrated by boosting surface-enhanced Raman scattering (SERS) efficiency by one order of magnitude through a heating-induced process. Our approach involves assembling gold nanoparticles with distinct dimensions, i.e. 16 and 80 nm, into well-defined planet–satellite-type arrangement structures using thermoresponsive (poly(N-isopropylacrylamide)) star polymer linkers. Insights into the assembly process were obtained by calculations within the Derjaguin–Landau–Verwey–Overbeek (DLVO) theory framework. We observe one order of magnitude increase in SERS enhancement by a heatinginduced volume-phase transition. This magnification aligns with simulations run using the finite-difference time-domain (FDTD) method. The implications of this adaptive supracolloidal concept are twofold: Firstly, our approach bypasses limitations of existing systems that are associated with the limited accessibility of electromagnetic hot-spot sites in strongly coupled, static assemblies of plasmonic nanoparticles, by providing the capability of dynamic hot-spot re-configuration. Second, these externally activated probes offer promising opportunities for the development of messenger materials and associated sensing strategies.