Small-fused acenes with an electron-donating alkoxyl naphthyl end-capper, which can tune the electronic properties and increase stacking by self-assembly, are synthesized by a simple process and fabricated into organic thin film transistors. In particular, hexyloxynaphthalene-end-capped anthracene, AN-ANE (see figure), shows field effect mobility three times that of pentacene under optimized conditions.