In order to enhance the microwave absorption performance, the multi-phase nanocomposites composed of magnetic medium and carbon nanotubes (CNTs) is designed and developed based on impedance matching. In this paper, LaFeO3/Fe@CNTs nanocomposites are prepared in situ using LaFeO3 as catalysts and C2H2 as carbon sources with CVD method, and then the microstructures, magnetic properties and microwave absorption performance are investigated in detail. The specific surface area of LaFeO3/Fe@CNTs nanocomposites increases greatly from 16.39 m3/g for LFC0 to 52.29 m3/g for LFC5 with the increasing CNTs content due to the enhanced heterogeneous interfaces. Ms also increases from 0.68 emu/g for LFC0 to 10.24 emu/g for LFC5 from magnetic Fe nanoparticles. LFC5 exhibits the best microwave absorption properties with the minimum reflection loss of -38.758 dB and a broad effective absorption bandwidth of 2.32 GHz at 2.5 mm. Impedance matching is balanced by permittivity from CNTs and permeability from Fe nanoparticles. Owing to the conductive CNTs with more defects, the dielectric loss and eddy current loss both increases to some extent. The synergistic loss mechanism of magnetic Fe nanoparticles and dielectric CNTs result in impedance matching and outstanding microwave attenuation.