Two asymmetrically substituted dicyanovinyl heterotetracenes are synthesized and characterized. Single-crystal X-ray diffractions indicate both intermolecular hydrogen bonds and pi-stacking existing in the solid-state structures. The solvatochromic behaviors of the two heterotetracenes were investigated in a variety of solvents. Both experimental and computational results suggest that the two heterotetracenes have low-lying lowest unoccupied molecular orbitals and thus may be potential n-type or bipolar organic semiconductors for organic electronics.