Intercalating redox active molecules into layered materials expands their functionality for emerging energy technologies. However, the mechanism of charge transfer to and from these small molecules within the confined environment of the layered host material and their role in charge storage are largely unexplored. Herein we examine charge transfer processes in metallocene intercalated transition metal dichalcogenides, including MoS2 and WS2. Combining experimental and computational analyses, we explore the orientation of the metallocene as a function of substitution pattern and study the influence of the metallocene redox potential on the electronic structure of MoS2 and WS2. We further examine the electrochemical response of these intercalated compounds via cyclic voltammetry. Our results show that the intercalated metallocene remains redox active and its redox potential is dramatically affected by the speciation and concentration of cations in the electrolyte. Our work provides a general strategy for studying the electronic and electrochemical responses of redox active intercalants in layered materials and highlights emergent phenomena regulating charge transfer that may be useful in energy storage and catalysis.