We have attempted to combine a gel and a solvent-free polymer electrolyte through the concept of the pore-filling polymer electrolyte; instead of using organic solvents, a viscous poly(ethylene oxide-co-ethylene carbonate) (P(EO-EC)) complexed with a LiCF3SO3 is filled into the pores of a porous poly(vinylidene fluoride-co-hexafluoropropylene) (P(VdF-HFP))/P(EO-EC) blend membrane. Our results indicated that the ionic conductivity of the pore-filling polymer electrolytes showing Arrhenius temperature dependence reached a maximum value of 3.7 x 10(-5) S cm(-1) at 298 K for E-V6E4, where "E-VxEy" denotes the Electrolyte of P(VdF-HFP)/ P(EO-EC) porous matrix (x/y by wt %) filled with the P(EO-EC)/LiCF3SO3 (in the case of E-V6E4, ca. 61 wt %). In this study, the Li-ion mobilities of a series of pore-filling E-VxEy polymer electrolytes were determined from Li-7 solid-state NMR line width and spin-lattice relaxation time measurements and were correlated with their ionic conductivities in conjunction with the effect and role of the amount of the P(EO-EC)/Li-salt electrolyte. In Li-7 NMR line width measurements, the onset temperature of Li-7 motional line narrowing was correlated with the glass transition temperature, T-g, of P(EO-EC) complexed with the Li-salt. Temperature dependence of correlation times, tau(c)'s, determined from Li-7 NMR line width data analysis with the Bloembergen-Purcell-Pound (BPP) theory for all polymer electrolytes, was composed of two distinctive regions above and below T-sc (temperature at slope change, 272-280 K), in which each region showed a linear Arrhenius behavior. In Li-7 NMR spin-lattice relaxation time in the rotating frame, T-1 rho, experiments, T-max's (temperature at T-1 rho(-1) maximum, 266-276 K) of the polymer electrolytes appeared to have a trend to shift to lower temperatures with increase of the amount of the P(EO-EC)/LiCF3SO3 electrolyte, indicating that the Li-ions were more mobile. Because the temperature dependence of the T-1 rho(-1) exhibited maxima, the correlation times, tau(c)'s, were able to be calculated using the BPP equation. For the temperatures above T-sc and T-max, which were the same temperature region where ionic conductivity measurements were carried out, the correlation times, tau(c)'s, and the corresponding activation energies, E-a's, obtained from both Li-7 line width and T-1 rho measurements decreased with increase of the amount of the P(EO-EC)/Li-salt electrolyte. From these results, it was concluded that the Li-ion mobilities of a series of pore-filling polymer electrolytes depended on the P(EO-EC)/Li-salt electrolyte content at the same temperature range from 280 to 340 K and enhanced Li-ion mobilities led to the increase of ionic conductivity, implying that Li-ion mobilities in polymer electrolytes had a strong correlation with their ionic conductivities.