Organic dyes usually exhibit enhanced photostability when trapped inside sol-gel silicates. The enhanced photostability is attributed to the reduction of intramolecular motions that facilitate photodegraclation. We report the simultaneous detection of mobility and photostability of sol-gel encapsulated didodecyl3,3,3', 3'-tetramethylindocarbocyanine (Dil) using single molecule spectroscopy. Fluorescence from Dil was resolved into parallel and perpendicular polarization components and separately detected. On the basis of the calculated fluorescence polarization, single Dil molecules were classified into "tumbling" and "fixed". Out of 212 molecules investigated, 52% were found to be fixed. For the first time, the mobility of a guest molecule in sol-gel silicate can be directly correlated with its own photostability. Both tumbling and fixed molecules have shown to exhibit nonuniform photostability, indicative of the very heterogeneous guest-host interactions within each subgroup. The survival lifetimes for the majority of the tumbling and fixed molecules were found to be 4.3 and 13.1 s, respectively, demonstrating unequivocally that fixed molecules exhibit a higher photostability than tumbling molecules. These results are in accordance with a recent study on rhodamine B encapsulated in dried sol-gel silicates.