A broadband cholesteric liquid crystal (CLC) device with a multi-domain structure is demonstrated by using an aggregation of polyhedral oligomeric silsesquioxane (POSS) nanoparticles in the CLC layer. The aggregation pattern of the self-assembled POSS nanoparticles depends on the concentration of POSS doped in the mixture of POSS/CLC and the cooling rate of the mixture from a temperature higher than the clear point. POSS-induced changes in the bulk and surface properties of the cholesteric cells, such as a promotion of homeotropic alignment, help to form a cholesteric structure with a broadband reflection of light; the latter can be used for improvement of bistable CLC devices. A higher POSS concentration and a higher cooling rate both improve the appearance of the black-white CLC device.