Cellular microenvironment and surrounding cells closely interact and interplay with each other. Understanding the cellular microenvironment is therefore important for investigation or manipulation of cellular behaviors. Using the substrates of photoreactions to modify short peptides, we have developed a series of hydrogelators that can form photoresponsive supramolecular hydrogels to mimic the cellular microenvironment and to support 2D/3D cell culture. Through using light to modulate the gel, we are able to manipulate cellular microenvironment and monitor the changes in both cellular microenvironment and cellular behaviors (Org. Biomol. Chem. 2017, 15, 6892; J. Am. Chem. Soc. 2013, 135, 18718).