An anthraquinone dye underwent supramolecular polymerization, affording 2D-monolayered nanosheets in a kinetically controlled state. The nanosheets then transformed into hierarchically chiral aggregates in a thermodynamically controlled step. The unanticipated role played by pathway complexity was clearly unravelled in this work, highlighting the diversified pathways in the supramolecular polymerization of various building blocks.