Spectrally active molecules are frequently utilized as probes of molecular systems and have been utilized to measure the properties of restricted environments created by lipid assemblies such as reverse micelles, liposomes, or lamellae. Generally, the molecular probes are chosen for their spectroscopic handles and the ability to interpret the observations made. Identifying the location of a molecular probe and its motions in confined environments is needed to understand the molecular system, recognizing that the location of a molecule dictates its motion and, in turn, affects molecular reactivity. We will use a several complementary spectroscopic methods to characterize the local environment sensed by a probe molecule within complex confined environments and to monitor probe motion within these environments. These methods include ultrafast laser spectroscopy, single molecule spectroscopy and NMR spectroscopy.