To examine whether the difunctionalization methodology could be expanded beyond diarylations, we envisioned the application of vinyliodonium salts to reach aryl(vinyl) sulfides. Literature routes to aryl(vinyl) sulfides primarily require thiophenols as sulfur source or employ transition metals to exploit the reactivity of disulfides. Thiiranes have been utilized to synthesize aryl(vinyl) sulfides from diaryliodonium salts with the common atomeconomy drawback caused by elimination of ArI. A primary objective for such methodologies is to ensure high E:Z selectivity, and our difunctionalization methodology would be an attractive and atom-efficient route to highly E-selective aryl(vinyl) sulfides under transition metal-free conditions.