Carbon nanotubes have shown great potential as conductive fillers in various composites, macro-assembled fibers, and transparent conductive films due to their superior electrical conductivity. Here, we present an effective defect engineering strategy for improving the intrinsic electrical conductivity of nanotube assemblies by thermally incorporating a large number of boron atoms into substitutional positions within the hexagonal framework of the tubes. It was confirmed that the defects introduced after vacuum ultraviolet and nitrogen plasma treatments facilitate the incorporation of a large number of boron atoms (ca. 0.496 atomic %) occupying the trigonal sites on the tube sidewalls during the boron doping process, thus eventually increasing the electrical conductivity of the carbon nanotube film. Our approach provides a potential solution for the industrial use of macro-structured nanotube assemblies, where properties, such as high electrical conductance, high transparency, and lightweight, are extremely important.