This paper presents an alternative path for the synthesis of 5-thiatruxene and the synthetic approach for 5-azatruxene not known so far. A new method for 5-thiatruxene improves the overall reaction yield from 17.5 to 22.6%, diminishes the synthesis time and costs by reducing synthetic steps from 5 to 2, and simplifies the isolation of intermediate and final products. The overall reaction yield for 5-azatruxene is 32.4%. The typical reactivity of both aromatic systems is also demonstrated. Recent research results suggest the use of 5-thiatruxene as the acceptor subunit of soluble blue emitters.