New classes of eight sugar azobenzene derivatives containing aryl groups, such as phenol, resorcinol, and naphthol, have been designed, synthesized, and characterized based on different spectral techniques. These sugar derivatives are reported as organogelators, and they possess the ability of selective detection of Cu 2+ ions over other metal ions. Among the derivatives, the compound containing the naphthol moiety was found to be a good gelator with a low critical gelation concentration of 1% in a mixture of DMF/H 2 O (1:1 v/v), and the existence of weak interactive driving forces in the self-assembled state was identified by using variable-temperature NMR and absorption studies. The sol−gel transition of these sugar-based low-molecular-weight gelators in the presence of copper (II) metal ions was investigated. It shows the metal sensing ability toward various metal ions in its solution state, and it was studied by using colorimetric, absorption, and emission spectroscopic techniques in DMF/H 2 O (7:3, v/v). Upon addition of a copper (II) solution, a drastic color change from orange to pink has been observed, which may be due to the formation of 1:1 complex formation as observed from Job's method, NMR, and density functional theory studies.