Two tetrabrominated intermediates obtained by bromination of naphthodithiophene in different solvents were used to construct novel highly 蟺-extended butterfly-shaped heteroarenes 1鈥?b>6, containing either an 8- or 10-fused ring. The solution-processed organic field-effect transistors based on compound 1 exhibited promising device performance with a hole mobility of 0.072 cm2 V鈥? s鈥? and a current on/off ratio of 106 under ambient atmosphere.