Arsenic-containing heteropentacenes were synthesized for the first time; bibenzofuran, benzothienyl benzofuran, and bibenzothiophene were bridged by arsenic atoms. Their structures and properties were experimentally and computationally studied using X-ray crystallography, optical and electronic properties, aromaticity, charge carrier mobility, etc. The present findings on the novel class of heteroacenes will expand functional organic chemistry.