In the present study, a pectin-like apple polysaccharide (AP) obtained by metal precipitation technique was demonstrated to show strong gelling capacity in the presence of K+ ion upon cooling. Increasing amount of K+ addition monotonically promoted the gelation of AP, as characterized by the increased gelation temperature (Tgel), gel melting temperature (Tmelt) and the gel strength. Compared with K+ ion, Na+ was unable to induce AP gelation even at high ionic concentrations, but other monovalent cations (Rb+, Cs+) can induce the gelation as in the case of K+ addition. At room temperature, the minimum cationic concentration as required to induce AP gelation followed the order of K+ ≈ Cr+ (8 mM) > Rb+ (3.5 mM), indicating that cationic radius (Na+ < K+ < Rb+ < Cs+) played a dominant role in inducing AP gelation, but other factors may also be involved. Finally, the gelation behavior of AP in the presence of K+ was explained as the suppressed intermolecular electrostatic repulsion between AP chains due to the strong electrostatic shielding effect of K+, which led to the formation of a gel network mediated by intermolecular hydrogen bonding. This reported gelation property may allow AP to find application as a new gelling polysaccharide.