Based on the chemical modifications of the few-layer boron nitride nanosheets (BNNSs) prepared by ball milling, several BNNS/polyurethane (PU) composite films (non-laminated films) were prepared by solution blending. It showed that the modified BNNSs (M-BNNSs) in PU matrices assembled into boron nitride (BN) micro-flakes and mildly orientated along the film planes. Then, an approach of multi-folding and multi-laminating further pro-moted the orientation, stacking and connection of BN micro-flakes, by which a three-dimensional (3D) BN network composed of lamellar BN skeleton and a small number ...