High molecular weight poly(9,10‐bis(p‐(2‐ethylhexyloxy)phenyl)‐2,6‐anthracenevinylene) (2,6‐PAV) was synthesized with 2,6‐dimethylanthraquinone as a key intermediate. The as‐synthesized polymer is readily soluble in common organic solvents and can be used for spin‐coating. The as‐synthesized polymer exhibits a broad absorption band ranging from 280 to 520 nm and a bluish green emission band with a peak at 500 nm. The polymer shows good thermal stability, and no distinct glass transition is observed. A simple device with the configuration ITO/PEDOT:PSS/2,6‐PAV/Ba/Al showed a turn‐on voltage of 4.8 V and a maximal brightness of 340 cd · m−2.