The photophysics of a complex between cucurbit[7]uril (CB7) and rhodamine 6G (R6G) was investigated using single-molecule spectroscopy. On the basis of the distribution of fluorescence intensity, two stable conformations of the CB7/R6G complex were identified. Both exhibit enhanced fluorescence relative to R6G alone. The two conformations are attributed to a flexible inclusion complex of R6G in CB7. Our single-molecule measurements also indicate that the photostability of R6G upon complex formation improves by 13x as opposed to 1.5x reported from ensemble measurements. The simplicity of using CB7 to enhance the fluorescence performance of a fluorophore makes it a promising strategy to deliver better probes for single-molecule spectroscopy in physical and life sciences research.