The synthesis, optical properties and thermal behaviour of three novel non-conventional 3,4,9,10-tetrasubstituted perylene-based discotic oligomers are reported for the first time consisting of a perylene core attached to which are four 4-cyanobiphenyl, triphenylene and cholesteryl units via flexible alkyl spacers. All the oligomers self-assemble into a mesophase and exhibit excellent fluorescence emission properties making them suitable for various opto-electronic applications.