Spectroscopic and photophysical properties of two p-phenylenevinylene (PV) trimers, 2,5-substituted diheptyl-(p-phenylene-vinylene) and di-[(2-ethylhexyl)oxy]-(p-phenylenevinylene), were studied using absorption spectroscopy, fluorescence and laser flash photolysis. The change from alkyl to alkyloxy groups red-shifts the absorption and fluorescence bands. The rate of internal conversion is independent of the substitution, whereas alkyloxy substitution increases the S-1 curved right arrow T-1 intersystem crossing rate by an order of magnitude. The relevance for the behaviour of conjugated PPV polymers is discussed. For diheptyl-PV, a sample having ca. 3%, of the cis-configuration was also studied. Comparison between the all-trans and the cis-contaminated samples revealed no significant differences in their photophysical properties. (C) 2004 Elsevier B.V. All rights reserved.