Two bichromophoric molecules consisting of anthracene and diphenylpolyene moieties Linked by two fused norbornyl bridges undergo photoionization upon ultraviolet (UV) pulsed laser irradiation. The simultaneous observation of the cation radicals of both anthracene and polyene groups points to a rapid (nanosecond or faster) intramolecular hole transfer equilibrium between the two chromophores. The existence of an equilibrium is supported by the results of one- and two-laser transient absorption and electrochemical experiments. Equilibrium constants (293 K) were determined:by both transient absorption and cyclic voltammetry measurements and were independent of the method used within experimental error. For A-sp-VB, which contains anthracene and vinyldiphenylbutadiene chromophores, K-eq = 4.0 +/- 2 (transient absorption) and 3.2 +/- 2 (electrochemical), favoring the anthracene cation radical. For A-sp-VS, containing anthracene and vinylstilbene groups, K-eq 70 +/- 30 (transient absorption) and 105 +/- 50 (electrochemical), favoring the anthracene cation radical.