A brief review is presented on fluorescence spectroscopy of molecules in the vicinity of a microstructure, which could be a surface structure, clustered ions/atoms, a colloidal particle in a solution, or a tip in certain molecular probes. This structure can be viewed as microscopic, mesoscopic or macroscopic, depending on the specific environment in which the molecule is located. An overview is given for selected experimental and theoretical aspects of this phenomenon, emphasizing some of the previous modeling work of the authors. Discussion of possible future attempts to explore the phenomenon in more detail is presented at the end.