Room-temperature ionic liquids (RTILs) constitute a fine-tunable class of :compounds. Morpholinium-based cations are new to the field. They are promising candidates for electrochemistry, micellitation, and catalytic applications. We investigate halogenation (fluorination and chlorination) of the N-ethyl-N-methylmorpholinium cation from the thermodynamics perspective. We find that substitutional fluorination is much more energetically favorable than substitutional chlorination, although the latter is also a permitted process. Although all halogenations at different locations are possible, they are not equally favorable. Furthermore, the trends are not identical in the ease of fluorination and chlorination. We link the thermodynamic observables to electron density distribution within the investigated cation. The reported insights are based on the coupled-cluster technique, which is a highly accurate and reliable electron-correlation method. Novel derivatives of the morpholiniurn-based RTILs are discussed, motivating further efforts in synthetic chemistry.