A simple and highly efficient method for synthesis of benzoxazoles, benzimidazoles, and oxazolo[4,5-b]pyridines is described. Condensation of orthoesters with o-substituted anilines or 2-amino-3-hydroxypyridine was performed in the presence of catalytic amounts of commercially available, inexpensive, and moisture-stable 1,3-dibromo-5,5-dimethylhydantoin under solvent-free conditions. The corresponding heterocycles were obtained in good to excellent yields. The main advantages of the present procedure are mild reaction conditions, short reaction times, high yields of products, easy work-up, and absence of solvent.