Interesting physicochemical properties of the room‐temperature ionic liquids (RTILs) have attracted considerable attention during the last decade. These were originally considered as potential benign (environment‐friendly) alternatives to the volatile organic compounds, which are used in chemical and industrial applications and significantly contribute to pollute our environments. Although these materials are not so green as thought originally, a huge potential of these substances in varied applications has been demonstrated. Considering that only a limited number of possible ionic liquids have so far been explored, the development of new ionic liquids and their physicochemical studies have been remaining as an active area of research. Recently, developed morpholinium ion‐based ionic liquids have been found to be promising. They remain largely unexplored, and we have recently initiated studies on morpholinium ionic liquids. Our studies are based on steady‐state and time‐resolved fluorescence behavior of dissolved solutes in these media. They are highlighted in this chapter. We discuss the excitation wavelength dependence of some dipolar fluorescence probe molecules in these ionic liquids and compare these findings with those in other ionic liquids to show that these are more structured or heterogeneous at the microscopic level than some commonly used ionic liquids based on imidazolium ions. We also present the results on time‐resolved fluorescence Stokes shift and time dependence of the fluorescence anisotropy of the probe molecules not only to investigate the dynamics of solvent and rotational relaxation in these media but also to substantiate a more organized structure of these ionic liquids.