The effective identification of the active catalytic phase is essential to elucidate the growth mechanism of boron nitride nanotubes (BNNTs) and realize their controllable and scalable synthesis. However, owing to the complexity of chemical reactions during BNNT growth via chemical vapor deposition (CVD) and the lack of techniques for in situ characterization at high temperatures (1100-1300 degrees C), identifying the true catalyst during BNNT growth is challenging. Herein, an aluminum (Al)-based active catalyst for BNNT growth via CVD is investigated. The initial Al2O3 nanoparticle catalyst precursor is transformed into an Al-B phase prior to BNNT growth. Based on our density functional theory-based molecular dynamic simulations of BNNT nucleation, AlBx (x = 1.5 to 2) shows catalytic activity for the formation of BN chains and BN six-membered rings. Confirmatory experiments demonstrate that AlB2 is the active Al-based catalyst during BNNT growth. A nanocomposite is prepared from cellulose nanocrystal, and purified BNNTs exhibited a high in-plane thermal conductivity of 13.33 W m(-1) K-1 at 20 wt% BNNTs. A further application for light-emitting diode chip cooling demonstrates excellent heat-dissipation performance of the nanocomposite film. Thus, this study can guide the controllable synthesis of high-quality BNNTs and facilitate their use in thermal interface materials.