The effects of micellar solubilization on excitedstate properties of several retinyl polyenes have been examined primarily by nanosecond laser flash photolysis. The relative intensity of band system III (254-256 nm) in the ground state absorption spectrum of 11-cis retinal decreases significantly on going from methanol to micellar solutions, suggesting that the 12-s-trans form of 11-cis retinal is relatively favored in the organized media. In addition to microsecond transient phenomena due to triplets, the laser flash photolysis of all-trans and 11-cis retinal and alltrans retinyl Schiff base incorporated into micelles leads to 'permanent' absorption changes attributable to photoisomerization (in the case of retinals) and protoaation and/or complexation with water (in the case of Schiff base). Alltrans retinol and retinyl acetate in micellar solutions undergo ionic photodissociation leading to long-lived retinyl carbocation (A,~~ = 585-600 run), the process being monophotonic in the case of retinyl acetate and predominantly biphotonic in the case of retinol. Tpe+&rends i the location of ground-state absorption maxima ( B <____ P A 1 and triplet yield of retinals, and photodissocYation yield of retinyl acetate suggest that the polarity of the environment probed by the polyene systems increases in the order: Triton X-100 < C'TAB < NaLS.