All multiwall carbon nanotube (MWNT) thin films are created by layer-by-layer (LBL) assembly of surface functionalized MWNTs. Negatively and positively charged MWNTs were prepared by surface functionalization, allowing the incorporation of MWNTs into highly tunable thin films via the LBL technique. The pH dependent surface charge on the MWNTs gives this system the unique characteristics of LBL assembly of weak polyelectrolytes, controlling thickness and morphology with assembly pH conditions. We demonstrate that these MWNT thin films have randomly oriented interpenetrating network structure with well developed nanopores using AFM and SEM, which is an ideal structure of functional materials for various applications. In particular, electrochemical measurements of these all-MWNT thin film electrodes show high electronic conductivity in comparison with polymer composites with single wall nanotubes, and high capacitive behavior with precise control of capacity.