Introducing carbon nanotubes (CNTs) capable of anchoring on nanofibers establishes new possibilities in many applications, such as lithium–sulfur bat- teries and laminated composites. Direct growth and attachment of CNTs elim- inate dispersion challenges such as detachment or transfer of CNTs onto another medium and damage to CNTs, making them inadequate for practical applica- tions. This study facilitated the direct growth of conductive CNTs on curved, high-temperature resistant polymeric polybenzimidazole (PBI) nanofiber sur- faces via chemical vapor deposition (CVD). Control of CVD process parameters, including nucleation and growth times (10 or 15 min) and catalyst concentration (1 or 10 mM) at 600 °C resulted in the growth of radially oriented CNTs on PBI nanofiber surfaces and provided morphology-dominated behavior both on physical and electrical properties. Morphological analyses showed that opti- mizing catalyst concentration (10 mM) and CVD process parameters, including nucleation (15 min) and growth times (10 min and 15 min), yielded uniform CNT coverage and conformity. A systematic exploration of mesoscopic mor- phologies revealed a strong correlation between physical parameters such as CNT array lengths and electrical conductivity, up to 0.039 ± 0.004 S/cm. The proposed CNT growth method could offer in situ structural tunability to respond to application-related requirements from energy storage to the rate capability of lithium-based batteries.