An exploratory study on a group of silylethynylated N-heteropentacenes as soluble and stable organic semiconductors is presented. An interesting finding is that a silylethynylated N-heteropentacene can function as a p-type, n-type, or ambipolar organic semiconductor depending on the structure of its pi-backbone. The tetraazap-entacene derivative is one of the best performing n-type organic semiconductors with an electron mobility of up to 3.3 cm(2) V-1 s(-1).