It is very challenging to realize well-controlled structural transformations in artificial supramolecules. Herein we report the construction of a novel family of multi-bisthienylethene hexagons with precise control of the shape and size as well as the specific number of photochromic units via coordination-driven self-assembly. These newly developed multi-bisthienylethene hexagons are highly sensitive and responsive to photostimuli, especially allowing for quantitative reversible supramolecular transformations triggered by light irradiation.