Highland barley, a nutritious whole grain, faces limited market utilization due to the poor heating stability of its starch. The aim of this study was to investigate the effects of three differently charged ionic polysaccharides—guar gum (GG), xanthan gum (XG), and carboxymethyl chitosan (CMC)—on the gel properties of highland barley starch (HBS). GG and XG notably increased pasting viscosity, viscoelasticity, hardness, and strength of HBS gels. Conversely, CMC resulted in decreased gel properties. All three polysaccharides enhanced OH tensile vibration (3000–3800 cm−1), with GG and XG promoting denser honeycomb network structures and lower spin–spin relaxation time (T2), indicating improved structural integrity. In contrast, low concentrations of CMC led to disorder and loose structure. Hydrogen bonding and electrostatic interactions were the main forces by which polysaccharides influenced the properties of starch gels. This research contributes to enhancing the properties of HBS gel during heating and expanding its commercial applications. It also provides some insights to understand the interaction between different charged polysaccharides and starch.