The addition of plasticizers into Li+-conductive solid polymer electrolytes (SPEs) is a commonly known technique to enhance the ionic conductivity. Among the used plasticizers, alkoxides of group-13 elements [such as poly(ethylene glycol) (PEG)–borate ester] are promising candidates due to the Lewis acidity of the elements of this group (i.e. B, Al, and so on), which interact with the anions and may increase the degree of dissociation of the salts and the transport number of the SPEs. By means of pulsed-gradient stimulated-echo NMR (PGStE-NMR) and AC impedance measurements, we investigate the effect of Lewis acidity originated from group-13 elements on the transport number and the dissociation rate of SPEs containing various plasticizers. Our results show that the degree of salt dissociation is significantly enhanced by the addition of plasticizers including group-13 elements, whereas only a small or negligible increase of the transport number is observed for these SPEs. We infer that the plasticizers exhibiting Lewis acidity associate with the anions, and that the associated pairs can migrate in the SPEs as fast as free anions, which results in a lower transport number than expected.