In this work, halogen bonding interactions in the complexes of two new nitroxide radicals, which contain both a halogen-bond-donor group and an electron-spin resonance -active radical unit, were investigated using density functional theory calculations. For comparison, the corresponding hydrogen-bonded complexes were also examined. Halogen bonds in these systems are predicted to be linear and much stronger than hydrogen bonds. To further understand the nature of these interactions, many theoretical methods, such as atoms in molecules, noncovalent interaction index, localized orbital locator, energy decomposition analysis, electron density difference, and electron spin densities, were employed. Compared with hydrogen bonds, halogen bonds have more open shell and covalent interaction components. Particularly, the formation of halogen bonds changes the ratio of different conformations, leading to spin density shift on certain atoms. The results reported herein will assist in the design of new functional probes for the detection of halogen bonding.