AbstractA novel efficient synthesis of fluorescent, fused quinoxalines was achieved. 7‐Triazolyl‐1,4‐dioxino[2,3‐b]‐quinoxalines were synthesized by the diazotisation of 7‐amino‐1,4‐dioxino[2,3‐b]quinoxaline and coupling with selected aromatic amines followed by air oxidation. Diazotised aryl amines were coupled with 7‐amino‐1,4‐dioxino[2,3‐b]quinoxalines followed by subsequent air oxidation afforded 1,4‐dioxino[2,3‐b]quinoxalino‐[6,5‐d]1,2,3‐triazoles. 7‐Amino‐1,4‐dioxino[2,3‐b]quinoxaline was condensed with conjugated enol ethers followed by cyclization in dowtherm resulted in 1,