Native functionality directed the C-H activation cascade to enable rapid construction of molecular complexity, featuring step-economy and synthetic efficiency. Herein, by exploiting bifunctional α-alcohol haloalkynes, we developed Ru(II)-catalyzed carboxylic acid, amine, and amide assisted divergent C-H alkynylation and annulation cascade, affording polyfunctional heterocycles. Significantly, a bilateral aryl C-H polycyclization cascade of azobenzenes was achieved using the versatile haloalkynes.