This work explores the use of hexagonal boron nitride (h-BN), a graphite-like compound, as a novel catalyst with base and acid functionalities. For use as a solid catalyst, the layered structure of h-BN was disrupted by ball-milling, exposing boron and nitrogen edge sites as well as increasing the surface area from 3 to ca. 400 m(2) g(-1). Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and proton magic-angle spinning nuclear magnetic resonance spectroscopy (H-1 MAS NMR) indicated simultaneous and adjacent formation of amino and hydroxyl groups by milling, which function as Bronsted base and acid sites, respectively. Analysis using color indicator reagents and pyrrole-adsorbed H-1 MAS NMR results revealed that the ball-milled h-BN had basic sites of strength +9.3 > H_ >= +7.2, comparable to those of KY zeolite. Measurements of P-31 MAS NMR of adsorbed trimethylphosphine oxide indicated that the ball-milled h-BN had weak acid sites, comparable to those in HY zeolite. Despite its weak basicity, the ball-milled h-BN showed high activity and selectivity toward beta-nitroalkenes for the nitroaldol reaction (Henry reaction) and the Knoevenagel condensation, whereas nontreated h-BN did not show activity. The nitroaldol reaction was considered to proceed in two steps: the abstraction of a proton from nitro methane by the amino group and the formation of an imine followed by a nucleophilic attack of the deprotonated nitromethane. Kinetic isotope effect experiments using (D)-substituted nitromethane revealed that the first step was the rate-determining step. Several nitroaldol reactions using a variety of monosubstituted benzaldehydes indicated that electron-donating groups enhanced the activity, suggesting that the formation of adjacent base and acid sites is responsible for it. This study shows the high catalytic activity of BN, a solid catalyst with moderate basicity and weak acidity. (C) 2017 Elsevier Inc. All rights reserved.