To address challenges in heat dissipation and electromagnetic compatibility in miniaturized electronic devices, this study reports the construction of a Ni-NiO heterostructure on fluorinated boron nitride (FBN).Ni-MOF was uniformly coated onto FBN via a solvothermal synthesis process, followed by high-temperature annealing to obtain FBN@Ni-NiO composites.The FBN@Ni-NiO-700 composite achieved exceptional performance, with a min. reflection loss (RLmin) of -67.64 dB at 2.87 mm thickness in the X-band and a maximum effective absorption bandwidth (EABmax) of 5.78 GHz.The Ni-NiO heterostructure synergistically enhances electromagnetic wave dissipation through magnetic and antiferromagnetic interactions and optimizes impedance matching, yielding broad absorption bandwidth.Also, with its innovative structural design and exceptional electromagnetic loss properties, the FBN@Ni-NiO composite demonstrates remarkable performance advantages, achieving an outstanding maximum RCS reduction of 19.82 dB m2.In TC, FBN@Ni-NiO-700/UV-cured resin composites achieved a 537 % increase, from 0.2500 W m-1 K-1 to 1.5915 W m-1 K-1 at 30 wt% filler content.This pronounced enhancement is ascribed to the formation of continuous and well-ordered thermal conduction pathways facilitated by the synergistic interplay between FBN and the Ni-NiO heterostructure, which significantly improves phonon transport efficiency.Addnl., the Ni-NiO interface effectively reduces phonon scattering between the thermal fillers and the polymer matrix.These results underscore the promising potential of FBN@Ni-NiO composites for applications in 5G communication systems, radar technol., and aerospace engineering.