In recent years, there has been an intensive growth in telecommunications and electronic industries, the electromagnetic pollution is getting serious due to increase in sensitivity of electronic devices and mutual interference among devices. To tackle the problem, the development of high-performance microwave absorption (MA) materials is considered. Employing carbon nanotubes (CNTs) with strong dielectric loss is an efficient way to improve the dielectric loss of the composites. However, sole CNTs suffer from a limited loss caused by the mismatch of interface impedance, which lead to reflect electromagnetic wave. The impedance matching characteristic of the CNTs can be optimized by the polyaniline (PANI) shell with an intermediate conductivity. Different from previous works that by incorporation of PANI into CNTs uniformly was through chemical functionalization, or destroying the original structure of CNTs to enhance the impedance matching characteristic of the composite. In this study, PANI was assembled on the surface of CNTs uniformly as a shell were synthesized in the presence of polyvinyl pyrrolidone (PVP), which is not only beneficial to the dispersibility of CNT, but mainly to be a steric stabilizer for getting PANI micelle and coated on the surface of the CNTs uniformly in polymerization process. The combination of CNTs and the PANI shell can overcome the contradiction of strong dielectric loss and impedance matching of CNTs. When the content of the CNTs/PANI composites is 10 wt%, the minimum value of the reflection coefficient can reach -41.5 dB at 9.5 GHz. Meanwhile, the effective absorption bandwidth (EB) of CNTs/PANI hybrids can reach 5.11 GHz at the thicknesses of 2 mm when the reflection loss reflection loss (RL) is lower than-10 dB. From mentioned above, these results promise a simple and effective approach to get a high-performance microwave absorption material.