The recent discovery of superconductivity with a transition temperature (T(c)) at 18 K in K(x)picene has extended the possibility of high-T(c) superconductors in organic materials. Previous experience based on similar hydrocarbons, like alkali-metal doped phenanthrene, suggested that even higher transition temperatures might be achieved in alkali-metals or alkali-earth-metals doped such polycyclic-aromatic-hydrocarbons (PAHs), a large family of molecules composed of fused benzene rings. Here we report the discovery of high-T(c) superconductivity at 33 K in K-doped 1,2:8,9-dibenzopentacene (C(30)H(18)). To our best knowledge, it is higher than any T(c) reported previously for an organic superconductor under ambient pressure. This finding provides an indication that superconductivity at much higher temperature may be possible in such PAHs system and is worthy of further exploration.