Here, a facile, low-cost, and high-efficiency method to construct a vertically aligned hexagonal boron nitride nanosheet (hBNN) thermal conduction channel structure is proposed to improve the thermal conductivity. First, exfoliated negatively charged BNNs and positively charged FeCo nanocubes self-assemble to form complex nanomaterials by strong electrostatic interactions. Then, the BNNs can orient with FeCo nanocubes in magnetic field, and the {001} facets of BNNs adsorb on the {100} facets of FeCo nanocubes. The large scale range and high-density FeCo/hBN-aligned structures are observed by scanning electron microscopy, which can act as thermal dissipation channels by conveying more phonons through a preponderant thermally conductive direction. The thermal conductivity of the composite films with 30 wt % FeCo and 50 wt % BN filler is 2.25 W m–1 K–1, 7 times higher than that of the films only containing 50 wt % randomly distributed hBN filler (0.325 W m–1 K–1) and 20 times higher than pure polydimethylsiloxane films (0.114 W m–1 K–1). The thermal management capability of the composite films is evaluated as a thermal conducting substrate of a light-emitting diode chip and the infrared thermal technology. Apart from the surprising thermal conductivity, FeCo–BNNs composite films also exhibit superb flexibility.