Two new ferrocene-containing triarylborane polymers have been prepared from trimethylsilyl-substituted polystyrene via selective polymer modification reactions with organometallic reagents. The photophysical and electrochemical properties of the polymers have been investigated and compared with the respective molecular model compounds. Cyclic voltammetry studies reveal reversible ferrocene-centered oxidation and boron-centered reduction processes at similar potentials as for the molecular species. In contrast, binding studies indicate a distinct polymer effect in that the molecular species show a much larger affinity for fluoride.