A study on the self-assembly of regiochemically differentiated methyl substituted quaterthiophenes is presented. Hierarchical self-assembly of 5,4',3 '',5'''-tetramethyl-2,2':5',2 '':5 '',2'''-quaterthiophene molecule, 7 leads to unprecedented fluorescent superstructures on glass and mica surfaces made by reiteration of a peculiar V-shaped recurring motif that extended at least for three generations. (C) 2009 Elsevier B.V. All rights reserved.