The ionic effects on synthetic polymers have attracted extensive attention due to the crucial role of ions in the determination of the properties of synthetic polymers. This review places the focus on specific ion effects, multivalent ion effects, and ionic hydrophilicity/hydrophobicity effects in synthetic polymer systems from solutions to brushes and gels. The specific ion effects on neutral polymers are determined by both the direct and indirect specific ion–polymer interactions, whereas the ion specificities of charged polymers are mainly dominated by the specific ion-pairing interactions. The ionic cross-linking effect exerted by the multivalent ions is widely used to tune the properties of polyelectrolytes, while the reentrant behavior of polyelectrolytes in the presence of multivalent ions still remains poorly understood. The ionic hydrophilicity/hydrophobicity effects not only can be applied to make strong polyelectrolytes thermosensitive, but also can be used to prepare polymeric nano-objects and to control the wettability of polyelectrolyte brush-modified surfaces. The not well-studied ionic hydrogen bond effects are also discussed in the last section of this review.