Self-assembled monolayers (SAMs) of redox-active molecules on mesoscopic substrates exhibit two-dimensional conductivity if their surface coverage exceeds the percolation threshold. Here, we show for the first time that such molecular charge transport layers can be employed to electrochemically address insulating battery materials. The widely used olivine-structured LiFePO4 was derivatized with a monolayer of 4-[bis(4-methoxyphenyl)amino]benzylphosphonic acid (BMABP) in this study. Fast cross-surface hole percolation was coupled to interfacial charge injection, affording charging and discharging of the cathode material. These findings offer the prospect to greatly reduce the amount of conductive carbon additives necessary to electrochemically address present metal phosphate cathode materials, opening up the possibility for a much improved energy storage density. When compared at equal loading, the rate capability is also enhanced with respect to conventional carbon-based conductive additives.