In this report, we have developed a scalable approach to massive synthesis of hexagonal/turbostratic composite boron nitride nanosheets (h/t-BNNSs). The strikingly effective, reliable, and high-throughput (grams) synthesis is performed via a facile chemical foaming process at 1400°C utilizing ammonia borane (AB) as precursor. The characterization results demonstrate that high quality of h/t-BNNSs with lateral size of tens of micrometers and thickness of tens of nanometers are obtained. The growth mechanism of h/t-BNNSs is also discussed based on the thermogravimetric analysis of AB which clearly shows two step weight loss. The h/t-BNNSs are further used for making thermoconductive h/t-BNNSs/epoxy resin composites. The thermal conductivity of the composites is obviously improved due to the introduction of h/t-BNNSs. Consideration of the unique properties of boron nitride, these novel h/t-BNNSs are envisaged to be very valuable for future high performance polymer based material fabrication.