Hydrophobically modified ethoxylated urethanes (HEURs) belong to an important class of telechelic associative polymers for improving solution rheological properties. We designed and prepared a novel azobenzene end-functionalized HEUR polymer (AzoHEUR), which was used to investigate the effects of hydrophobicity change of end hydrophobes induced by photoisomerization of azobenzene on the solution aggregation and rheological properties. The concentrated AzoHEUR solutions show a reversible rheological property change upon alternative exposure to UV and visible light. We have demonstrated that a reversible change in hydrophilic lipophilic balance of polymer followed by photoisomerization of azobenzene induces a reversible rearrangement of micellar junctions through loop-bridge or bridge-loop transitions, which reversibly changes not only the network connectivity but also the solution relaxation behavior. Moreover, a structural model is proposed to describe the rearrangement of micellar junctions induced by photoisomerization of azobenzene. The work will not only provide new insights into the effect of hydrophobicity change of stimuli-responsive end groups on the aggregation and rheological behavior of HEUR aqueous solutions but also open a new perspective for development of some special applications of HEURs in fabrication and transmission of soft materials, medicines, cosmetics, inks for inkjet printers, and flow rate controlling systems.