Development of carbon fibers (CFs) with high strength and high modulus for structural applications in CF-reinforced polymer (CFRP) industry has been a challenge. Herein, we propose a method for manufacturing highly oriented polymer–carbon nanotube (CNT) composite fibers having high strength (4.8 ± 0.2 GPa), modulus (390 ± 48 GPa), and electrical conductivity (5.75 ± 0.84 MS m-1) by a liquid crystalline wet-spinning process. The use of chlorosulfonic acid (CSA) as a solvent for CNTs and polyimide (PI) promotes dispersion and enables the production of high-performance composite fibers. In addition, the functional groups of PI in composite fibers improve the interfacial shear strength with epoxy resin without sizing additives by 72% compared to that of CNT fibers. Carbonization and graphitization of the composite fibers with an optimal ratio of PI (30%) and CNT cause significant improvement in their mechanical (tensile strength; 6.21 ± 0.3 GPa and modulus; 701 ± 47 GPa) and thermal properties (496 ± 38 W m−1 K−1) by reducing voids and improving orientation. We believe that the polymer–CNT composites and their CFs with high strength and high modulus would be the next-generation CFs for aerospace and defense industry.