The structure of a solution of poly(methyl methacrylate)-block-poly(benzyl methacrylate-stat-(4-phenylazophenyl methacrylate)) in the ionic liquid 1-ethyl-3-methyl imidazolium bis(trifluoromethanesulfonylimide) can be controlled with light. We explored the phase behavior of this block polymer at a concentration of 30 wt % as a function of temperature. Remarkably, this solution shows ordering into hexagonally closed packed spheres (HCP) upon heating under visible light, as confirmed by small-angle X-ray scattering. Small amplitude oscillatory shear rheology was used to demonstrate that the system could readily be converted between HCP and disorder by switching between visible and UV light wavelengths at 100 °C. This switching was cycled six times, without any noticeable change in the ordered or disordered state. The dependence on illuminating wavelength arises from the changes in polarity of the azobenzene moiety, which modulates its solubility in this ionic liquid to a significant extent. This is the first example of reversible light-triggered ordering of a "coil-coil" block polymer, a phenomenon that has been previously observed only in liquid crystalline systems.