The influences of sodium chloride (NaCl)/sucrose on starch properties as affected by starch structural characteristics are little understood. In this study, the effects were observed in relation to the chain length distribution (from size exclusion chromatography) and granular packing (inferred through morphological observation and determination of swelling factor and paste transmittance) of starches. Adding NaCl/sucrose dramatically delayed the gelatinization of starch that had a high ratio of short-to-long amylopectin chains and had loose granular packing. The effects of NaCl on the viscoelasticity of gelatinizing starch were related to the flexibility of amylopectin internal structure. Effects of NaCl/sucrose on starch retrogradation varied with starch structure, co-solute concentration, and analytical method. The co-solute-induced changes in retrogradation were highly associated with amylose chain length distribution. Sucrose strengthened the weak network formed by short amylose chains, while the effect was not significant on amylose chains that were capable of forming strong networks.