Herein, a new fabrication method for CNT nanofiber composite (pPC-FP) through non-covalent interaction between porphyrin monomers with CNTs is reported. This led to the alleviated agglomeration of pristine CNT without acid pre-treatment, producing a highly porous material with high surface area of 444 m2/g and narrow pore size distribution for all pPC-FP nanofiber composites. Enhanced performances of pPC-FP3 and pPC-FP5 (CNT nanofiber with porphyrin monomers) were brought about by the enhanced CNT dispersion, hence, better porosity as compared to pPC. Moreover, through the incorporation of porphyrin monomer, M-NC bond was simultaneously formed and served as a contributor to the excellent capacitive performance of the material, resulting in the highest capacitance of 150 A/cm2 at 0.25 mAh/cm2 with 77 A/cm2 at 2.5 mAh/cm2. The composites also exhibited stable performance even after cycling at different current densities (0.25–2.5 mAh/cm2) for 3000 cycles with almost 100% columbic efficiency. Through π-π stacking interaction, the agglomeration was prevented and CNT was aligned along the axis of the polymer which rendered the nanofibers highly porous resulting to a conductive composite material with excellent electrochemical performance.