The structure and properties (crystallography, NMR, theoretical calculations) of the three N-unsubstituted benzazoles (1H-benzimidazoles, 1H-and 2H-indazoles, 1H-and 2H-benzotriazoles) have been reviewed for the period 2000–2012 with some results from previous years. The study of these compounds will greatly increase in the coming years and it is expected that the present review will contribute to it. In 1974 we published a paper entitled "The benzazoles (benzimidazole, indazole, benzotriazole): molecular structure and fundamental properties" [1] where the three stable parent compounds 1, 6, and 12 were compared (Figs. 1-3, the possible tautomers of compounds 1, 6, and 12 were not reported in the solid state). Nearly forty years later the situation has much changed and thousands of papers and several books have been published on these heterocycles. This review will be limited to: 1) compounds bearing protons on the nitrogen atoms, NH-benzazoles (Figs. 1-3); 2) structural and theoretically calculated physicochemical properties (synthetic aspects, reactivity, and biological properties will not be discussed); 3) the literature will cover mainly the 2000–2012 period, and 4) all our main contributions, published or in press, will be reported.