Cracking is a widespread phenomenon throughout the service of concrete structures for marine and offshore engineering. In this paper, the effect of sulfate ions and related cations on the crack closure behavior of cracked mortar in chloride-containing environments was studied. To this end, the mortars are cracked before transferring to the pure chloride solution as well as composite chloride and sulfate solutions (CNS and CMS series). The self-healing behavior is assessed by the evolution of crack width, water absorption, and nondestructive ultrasonic detection. The Vickers hardness test is applied to evaluate the micro-hardness of self-healing products generated in the crack gaps. Thermodynamic modeling of the phase volume expansion from the mortar matrix to the crack surface is conducted using Gibb’s free energy theory to explore the self-healing mechanisms. Experiment results suggest that the existence of sulfate ions in chloride-containing solutions is beneficial for crack closure, and self-healing could be more obvious if the cations that bind to sulfate are magnesium ions. The distributions of Vickers hardness on the mortar surface across the crack reveal that the brucite layer diminishes the overall Vickers hardness of the mortar matrix, whereas it is favorable for the micro-hardness enhancement of self-healing products in the CMS series. Thermodynamic modeling interprets the expansion rates relative to the original unhydrated cement under the action of different soaking solutions.