We show that Landau-Zener tunneling in a small-gap insulator produces a singular DC current–voltage relation, and correspondingly, strong high-harmonic generation in AC transport. Remarkably, high-harmonic responses decrease subexponentially with harmonic order, which is parametrically slower than in ordinary conductors and PN diodes. We further derive a scaling law for the current amplitude at frequency nω produced by the applied electric field E at fundamental frequency ω. Our work offers a promising route to THz generation based on frequency multiplication in solids.