Oligomers and polymers of type [-CH2CHRCH2-(pi)-](n) comprising aryl units tethered by 2-substituted trimethylene were found to exist as a folding H-stacking structure in polar solvents such as CH3CN and in film, which was evidenced by their blue-shifted UV absorption compared to that of the parent aryl compounds, and exhibited predominantly excimer-like emission. In addition, annealing of the films resulted in a unique layered structure, which may arise from the folded polymer form.