The structural properties of the compound azobenzene were inspected utilizing x-ray diffraction. Azobenzene possesses a monoclinic crystal structure. The crystallite size, dislocation density and average micro-strain were determined for the most intense peaks (200), ( $$ \bar{1}10 $$ ), (400) and ( $$ \bar{1}02 $$ ). Optical properties of azobenzene solutions in dimethylformamide with different molarities were examined. UV–Vis spectra were recorded in the wavelength range 200–800 nm. The absorption coefficient analysis indicated that azobenzene experiences an optical transition of the allowed direct transition. Dielectric and AC electrical properties of a Au/Azobenzene/Au system were studied in the frequency range of (50–105 Hz) at specific temperatures. The convenient mechanism for AC electrical conduction in bulk azobenzene was correlated barrier hopping, with a maximum barrier height of 0.67 eV at 293 K. Further, the behavior of dielectric constant and dielectric loss as well as real and imaginary parts of complex electric modulus of bulk azobenzene were explored at certain temperatures.