Transition metal carbides/carbonitrides (MXene) exhibit huge potential as electromagnetic wave (EMW) absorbers in dealing with electromagnetic radiation problem that rise due to the rapid development of 5G era. The incorporation of magnetic materials can effectively mitigate the impedance mismatch and singular loss mechanisms inherent in pure MXenes (PMs). However, challenges persist due to issues such as random distribution, complex preparation processes, and inadequate interaction. In this study, Ti3C2Tx/Ni hybrids were synthesized using a one-pot method, wherein Ni, derived from molten salt, replaces Al layer of MXene, facilitating the in-situ growth of Ni nanocomponents within the interlayered region. The periodic electromagnetic synergetic network of “MXene-Ni-MXene-Ni-MXene” provides substantial magnetic resonance, eddy current loss, interface polarization, defect polarization, and dipole polarization, enriching the loss mechanism. By regulating the concentration of Ni, the intrinsic poor impedance matching of MXene was improved. Consequently, Ti3C2Tx/Ni hybrid exhibited exceptional electromagnetic wave absorption (EMA) performance, achieving a reflection loss (RL) of −64.51 dB and an effective absorption bandwidth (EAB) of 4.96 GHz at a matching thickness of 1.98 mm. Additionally, the super radar cross-section (RCS value = −15.73 dB m2) endow it potential in practical application. This work provides a facile method for achieving unique electromagnetic synergetic loss mechanism, thus paving the way for exploring high-efficient MXene-based EMW absorbers.