A range of silanylene-spaced divinylbenzene copolymers (1) and the corresponding monomers (2) have been synthesized by the rhodium-catalyzed hydrosilylation of the corresponding hisalkynes with bissilyl hydrides, and the photophysical properties of 1 and 2 have been investigated. The silicon moiety in 1 serves as an insulating tetrahedral spacer that makes 1 highly folded. The two chromophores may be in close proximity such that a ground-state intrachain interaction between two conjugated moieties through space might occur. (C) 2003 Wiley Periodicals, Inc.