Water-in-water droplets formed by liquid-liquid phase separations are a method of membraneless cellular compartmentalization, allowing a cell to quickly organize enzymes to respond to events without the high energy expenditure associated with forming membraned compartments. This organization drives increased catalytic rates of enzyme reactions. Though some of this surge can be attributed to localization and condensation of substrate and enzyme, it cannot account for the total increase. We hypothesize that the inner environ of a LLPS droplet provides a unique solvation environment compared to the bulk phase and should thus alter the thermodynamics of reactions within it. Using an extension of Marcus theory, we describe these effects which are observed in a shifted formal potential. Here, we demonstrate this proof of concept, employing fluorescent dyes as redox reporters: single-entity electrochemistry is used to quantify probes partitioned into LLPS droplets. These findings should aid biophysical explorations of these membraneless organelles of emerging interest and importance.