We report a facile synthetic protocol for preparation of dinaphtho[2,3-b:2′,3′-d]furan (DNF–V) derivatives. DNF–V derivatives showed high emissive behaviour in solid. A solution-crystallized transistor based on alkylated DNF–V derivatives showed an excellent carrier mobility of up to 1.3 cm² V⁻¹ s⁻¹, thereby proving to be a new solution-processable active organic semiconductor with high emission and high mobility.