We experimentally demonstrated the intrinsic nature of arsoles as promising functional heteroles. A series of 2,5-diarylarsoles are easily and safely prepared through the procedure in which non-volatile arsenic intermediates are employed to overcome the synthetic barrier due to the concern of volatility of the arsenic precursors used in conventional methods. A Pd-catalyzed Suzuki–Miyaura coupling reaction can be applied to the obtained arsoles for fine molecular design, unlikely to phospholes. It was demonstrated that the optical and electronic properties, i.e. emission colors, quantum yields, and energy levels of the frontier orbitals, are similar to those of phospholes, as conventional theoretical studies have predicted. Furthermore, it was found that arsoles showed mechanochromic properties.