Homogeneous and neutral clusters of tert-butyl nitrite [(CH3)(3)CONO](n), with (n) roughly 20, were produced by adiabatic jet expansion and photolyzed via the localized S-1(n pi(*)) <-- S-0 transition to R + NO ((2) Pi) at lambda(d) approximate to 360-400 nm. Using photofragment yield spectroscopy (PHOFRY), we determined the relative partial absorption cross sections leading to NO (nu" = 0, 1, 2) products from the monomer and the clusters which allowed us to selectively investigate from a monomer/ cluster mixture the cluster formation and the cluster photodissociation. The latter was further characterized by the rotational state distributions of the four sublevels of NO ((2) Pi(+/-1/2) and (2) Pi(+/-3/2)) and the rotational alignment A(0)(2)). Essentially two types of NO fragments emerged from the photoexcited clusters : one having relaxed J state distributions and no alignment A(0)((2)), the other hot (non-Boltzmann) distributions and a strong alignment as well as a preference for the Lambda-state A". The relaxed NO fragments are proposed to arise from nitrite molecules "solvated" in the cluster and the hot NO fragments from nitrite molecules with a free chromophore located on the surface of the cluster. The vibrational state population of NO appears no to be significantly influenced by cluster formation.