Ru(0)-catalysed cross-dimerisation and -trimerisation give a series of di- and triheteroaryl compounds cross-linked by π-conjugated trienyl groups. Their photochemical behaviour is studied using UV-visible absorption spectra, fluorescence emission spectra, and TD-DFT calculations. The cross-trimer prepared from 2,5-dialkynylthiophene with 2 equiv. of 2-butadienylpyridine shows a longer wavelength shift in the absorption maximum than the cross-trimer prepared from dialkynylbenzene with 1-phenylbutadiene. The solvent effect and the TD-DFT calculations suggest that the planarity of the π-conjugated system contributes more than spontaneous polarization. Namely, in the 5-membered thiophene ring, the conjugated trienyl group extends in the same plane (dihedral angle: -4.0°) as the thienyl group, whereas in the 6-membered benzene ring, the planarity is reduced due to steric hindrance (dihedral angle: -24.1°). Thus, the cross-trimers with a 5-membered heteroaryl centre contribute to longer wavelengths of absorption and fluorescence emission due to the increased planarity of the conjugated trienyl groups.