The purpose of this article is to find a way to prepare multiscale material, namely, carbon nanotube-hybridized carbon fiber (CNT/CF) with a low degradation of mechanical properties. Using a facile aerosol-assisted chemical vapor deposition method, a novel route was described to fabricate CNT/CF. The essential of this technique was in situ formation of catalyst (Fe) nanoparticles via pyrolysis of ferrocene-acetone aerosol right before CNTs growth. Through optimizing aerosol supply and process parameters, a uniform coverage of CNTs was successfully grafted onto the carbon fiber surface to obtain a multiscale (hierarchical) structure. The strong anchorage between the as-synthesized CNTs and carbon fiber substrate was confirmed by ultrasonic bath treatment. Compared with the as-received carbon fibers, single fiber tensile testing results demonstrated that the tensile strengths of CNT-hybridized carbon fiber slightly degraded within 10% at all the correspondingly given gauge lengths.