NiFe2O4/polypyrrole (NiFe2O4/PPy) nanocomposites are prepared by a simple surface-initiated polymerization method and demonstrate negative permittivity in the low frequency regions. These nanocomposites also exhibit significantly enhanced electromagnetic wave (EMW) absorption property in the high frequency regions. Compared with pure PPy, the enhanced negative permittivity is observed in the NiFe2O4/PPy nanocomposites with a NiFe2O4 loading of 5.0, 10.0, 20.0 and 40.0 wt%, indicating the formation of metal-like electrical conducting network in NiFe2O4/PPy nanocomposites. Moreover, the negative permittivity could be tuned by changing the NiFe2O4 loading. The minimum reflection loss (RL) of -40.8 dB is observed in the 40.0 wt% NiFe2O4/PPy composites with a thickness of only 1.9 mm. The effective absorption bandwidth below -10.0 and -20.0 dB reaches 6.08 and 2.08 GHz, respectively. The enhanced EMW absorption performance benefits from the improved independence matching, EMW attenuation capacity, and synergistic effects of conduction loss, dielectric loss (interfacial and dipole polarizations) and magnetic loss (exchange and natural resonances). This research work provides a guidance for the fabrication of nanocomposites with an excellent EMW absorption.