Electron donor−π−acceptor chromophores 5, 9, 11, 18−20, 21, 22, 27, 28a, 28c, 31, 32, 34−36, 38a−c, 41a, 41c, and 42 have been synthesised. The donor units are 1,3-dithiole and ferrocene; conjugated ethylenic, phenyl, phenylenevinylene, thienyl, bithienyl, terthienyl, or thienylenevinylene linkers act as a central π-electron relay unit, and dicyanomethylene and polynitrofluorene groups as the acceptor unit. The electronic absorption spectra display a broad low-energy intramolecular charge transfer band in the visible region (500−700 nm) the energy (hν ICT ഠ 1.7−2.5 eV) and intensity (ε ഠ 5000−50000 m −1 cm −1 ) of which depend substantially on the nature of both D and A moieties and on the structure of the linker unit. Nonlinear optical properties have been evaluated using the EFISH technique: the highest µβ (0) values are observed for 38b [(900±300)×10 −48 esu] and 42