Layer-by-Layer (LbL) deposition of electrochemically active materials on porous carbon electrodes is a proven method to leverage both electrochemical double-layer capacitance and pseudocapacitance for charge storage on the same electrode. LbL coatings are held together by electrostatic attraction between adjacent layers of oppositely charged molecules. Previous studies have used Keggin polyoxometalates to great effect as the anionic layer in LbL electrode modification, but little effort has been devoted to cationic material selection and LbL process optimization. This work investigated alternatives to the conventional, electrochemically inert polydiallyldimethylammonium (PDDA) cation. The use of fuchsin molecular cations in LbL deposition improved the specific energy and specific power of modified electrodes. Fuchsin cation also rendered the environmentally harmful oxidative surface activation step unnecessary for LbL deposition. Process parameters were optimized for MWCNT/Fuchsin/POM samples, and post-LbL electrochemical polymerization was found to further improve the performance of these electrodes.