Self-healing, ionically cross-linked networks were prepared from poly(acrylic acid) (PAA) and poly(triethyl(4-vinylbenzyl)phosphonium chloride) (P-Et-P), and their properties were studied. Three different ratios of PAA/P-Et-P were incorporated into the networks by varying the addition orders of the components. Swelling of the networks increased with increasing NaCl concentration when they were immersed in aqueous solution. All networks retained their structural integrity in 0.1 M NaCl. Studies of the rheological and tensile properties of the networks swelled in 0.1 M NaCl showed that PAA>P-Et-P exhibited high elongation and viscoelastic properties suitable for self-healing with a relaxation time of similar to 30 s, whereas the other networks exhibited predominantly elastic behavior. The moduli were similar to those of soft tissues. Self-healing of PAA>P-Et-P in 0.1 M NaCl was demonstrated through repair of a 0.5 mm diameter puncture in the material whereas healing was incomplete for the other networks and also for PAA>P-Et-P in the absence of NaCl. Healing after completely severing a tensile testing sample showed significant recovery of the modulus, strength, and elongation. The properties of these materials and their ability to self-heal in low and physiologically relevant salt concentrations make them promising candidates for a variety of applications, particularly in the biomedical area.