In this article, we discuss how fluorescence microscopy techniques are used to investigate important characteristics of porous silica materials. We start with a discussion of the synthesis, formation mechanism and functionalization of these materials. We then give an introduction to single molecule microscopy and show how this technique can be used to gain deeper insights into some defining properties of porous silica, such as pore structure, host-guest interactions and diffusion dynamics. We also provide examples from the literature demonstrating how fluorescence microscopy is used for elucidating important aspects of porous silica materials and heterogeneous catalysis, e. g. diffusion properties, reactivity, morphology, intergrowth, accessibility, and catalyst deactivation. Finally, a short outlook on the scope of porous silica hosts in drug delivery applications is given.