A new class of n-type semiconductors for organic thin film transistors (OTFTs), based on core-expanded naphthalene diimides fused with 2-(1,3-dithiol-2-ylidene)malonitrile groups, is reported. The first two representatives of these species, derived from long branched N-alkyl chains, have been successfully used as active layers for high-performance, ambient-stable, solution-processed n-channel OTFTs. Their bottom-gate top-contact devices fabricated by spin-coating methods exhibit high electron mobilities of up to 0.51 cm(2) V(-1) s(-1) with current on/off ratios of 10(5)-10(7), and small threshold voltages below 10 V under ambient conditions. As this class of n-type organic semiconductors has relatively low-lying LUMO levels and good film-formation ability, they also displayed good environmental stability even with prolonged exposure to ambient air. Both the device performance and the ambient stability are among the best for n-channel OTFTs reported to date.