The light-modulated isomerization and aggregation behavior of ionic liquids (ILs) in aqueous solutions holds fundamental and technological significance. Although several azobenzene-based photoresponsive ILs have been synthesized, there is still a lack of understanding regarding the aggregation mechanism, regularity of the alkyl chain length, and the position of the azobenzene (cis- and trans-) in these photoresponsive ILs. To elucidate the structure-property relationship of photoresponsive ILs, four types of azobenzene groups photosensitive ILs ([AzoC