Surface-tethered polymers are unique molecular architectures that have been recently used in advanced sensors, electronics and biomedical applications. However, techniques for characterizing these materials in their surfacetethered form remain limited. The incorporation of luminescent functionality into these materials has enabled new characterization methods, while also unlocking new applications in optoelectronics, stenography and sensing. Micronscale photolithography techniques have recently enabled the preparation of high-resolution patterns, as well as architectures with unique photophysical properties. Herein, we provide an overview of the techniques used to prepare luminescent polymer brush materials and their applications in stimuli-responsive sensors, cell adhesion materials, and optoelectronics. We also provide our perspective on the promising future uses of surface-tethered polymers, as well as the shortterm challenges and opportunities in the field.