The photochemical properties of stilbene cored amphiphilic dendrimers (G0-G3) in THF and water were investigated. The solvation dynamics in water depended on the generation, while the behavior is almost the same in THF. Dendrimers G1 and G2 form molecular assemblies and undergo photodimerization reaction in addition to photoisomerization. G3 has enough TEG groups on the surface to cover the hydrophobic moiety within a single molecule. These dendrimers have free space around the core to undergo mutual isomerization even in water. This type of surface functional group is important for the dendritic effect in water.