The synthesis of the novel alkyl-substituted helianthrones 8a, c and mesonaphthobianthrone 9 by photocyclization of the corresponding bianthronylidenes 7 a, b is described. Regioselectivity and scope of the photocyclizations of ?a and 7b depend on the substitution pattern. The structures of la and 8a have been established by X-ray crystallography and indicate an isomerization about the central double bond of la in the photoreaction. The structures of the protonated species of 8 a and 9 are elucidated, and their optical absorption and emission behavior is examined.