Benzo[b]arsole derivatives, being arsenic analogues of indole, were synthesized by utilizing a safely prepared arsenic precursor. The structural and photophysical properties of the obtained 2-arylbenzo[b]arsoles were experimentally and computationally studied in comparison with those of 1,2,5-triarylarsoles and 9-phenylarsafluorene. It was found that the emission color and/or quantum yield were significantly affected by substituents on the luminescent center and metal-coordination to the arsenic atom. This is the first study on the structure-property relationship of benzo[b]arsole derivatives.