Azobenzene (AZB is characterized by two phenyl rings connected by an azo linkage (-N=N-), that can exist in either the cis or trans conformations. This book provides new research on this chemical compound. Chapter One presents an overview regarding research progress and its reflections in applications of azobenzene-containing derivatives. Chapter Two reviews recent advances in hybrid azobenzene-silica materials. Chapter Three demonstrates the general concepts and potential applications of azobenzene-based liquid crystallines by understanding the relationships of molecular design-structural symmetry-morphological aspect-optical property. Chapter Four focuses on the synthesis, photo- and thermal isomerizations of azobenzenes incorporated in macrocyclic coordination compounds, and discusses the effect of macrocyclic structures on the isomerization of azobenzenes. Chapter Five studies wavelength dependence of polarized UV light induced supramolecular orientation of azobenzene-containing organic/inorganic hybrid materials of chiral Schiff base Ni(II), Cu(II) and Zn(II) complexes.