In this work, the optimal conditions of synthesizing and purifying carbon nanotubes (CNTs) from ferrocene were selected at the first stage, where decomposition time, argon fluxes, precursor amounts, decomposition temperature (at 1023 K and 1123 K), and purification process (HNO3 + H2SO4 or HCl + H2O2), were modulated through chemical vapor deposition (CVD) and compared to commercial CNTs. The processing temperature at 1123 K and the treatment with HCl + H2O2 were key parameters influencing the purity, crystallinity, stability, and optical/electrical properties of bamboo-like morphology CNTs. Selected multiwalled CNTs (MWCNTs), from 1 to 20 wt%, were electropolymerized through in-situ polarization with conductive polymers (CPs), poly(aniline) (PANI) and poly(pyrrole) (PPy), for obtaining composites. In terms of structural stability and electrical properties, MWCNTs obtained by CVD were found to be better than commercial ones for producing CPs composites. The CNTs addition in both polymeric matrixes was of 6.5 wt%. In both systems, crystallinity degree, related to the alignment of PC chains on MWCNTs surface, was improved. Electrical conductivity, in terms of the carrier density and mobility, was adequately enhanced with CVD CNTs, which were even better than the evaluated commercial CNTs. The findings of this study demonstrate that synergistic effects among the hydrogen bonds, stability, and conductivity are better in PANI/MWCNTs than in PPy/MWCNTs composites, which open a promissory route to prepare materials for different technological applications.