AbstractPorous solids often contain complex pore networks with pores of various sizes. Tracking individual fluorescent probes as they diffuse through porous materials can be used to characterize pore networks at tens of nanometers resolution. However, understanding the motion behavior of fluorescent probes in confinement is crucial to reliably derive pore network properties. Here, we introduce well‐defined lithography‐made model pores developed to study probe behavior in confinement. We investigated the influence of probe‐host interactions on diffusion and trapping of confined single‐emitter quantum‐dot probes. Using the pH‐responsiveness of the probes, we were able to largely suppress trapping at the pore walls. This enabled us to define experimental conditions for mapping of the accessible pore space of a one‐dimensional pore array as well as a real‐life polymerization‐catalyst‐support particle.