To study the cationic mobilities in pyrophosphate systems, ceramics pellets were prepared by mixing, then heating powders of Ca2P2O2 and Na4P2O7 at different vol.% Na4P2O7. The transport properties of such samples were studied as a function of temperature using complex impedance spectroscopy. It is shown that for 90 and 95 vol.% Na4P2O7 the samples exhibit strongly enhanced conductivity and dielectric constant. Taking into account structural and microstructural aspects, an interpretation is proposed.