Chromophore-modified bacteriorhodopsin (bR) analogs are prepared, to study the nature of chromophore–protein interaction as well as to develop new bR analogs that can find applications as photoactive element in molecular electronic devices. This article describes the preparation and characterization of hitherto unknown bR analogs based on diphenylpolyene chromophores. Diphenylpolyene compounds, namely, 4-[(E)-2-phenylvinyl]benzaldehyde (1), 3-methyl-5-{4-[(E)-2-phenylvinyl]phenyl}penta-2E,4E-dienal (2), 4-[4-phenylbuta-1E,3E-dienyl]benzaldehyde (3) and 3-methyl-5-{4-[4-phenylbuta-1E,3E-dienyl]phenyl}penta-2E,4E-dienal (4), have been synthesized, and their interaction with bacterioopsin (bOP) has been studied. Whereas aldehydes 2 and 4 interact with bOP and yield bR analogs bR-2 and bR-4, aldehydes 1 and 3 do not yield any pigment. Analogs bR-2 and bR-4 have been characterized for their opsin shift, competitive binding, photochemical properties and fluorescence spectral behavior.