Highly sodium deficient Na0.6NbO3 (NN) ceramics were prepared and characterized. Their mean structure could be described by a mixture of the predominant P polymorph (S.G. Pbma) and the Q phase (S.G. P21ma), at room temperature, as deduced from Rietveld refinements of Powder X-ray diffraction and Raman scattering data. Besides, microstructural and compositional heterogeneity was evidenced from HRTEM and XPS analyses. Dielectric measurements on this highly vacancies-containing NN material indicated a hysteretic transition taking place at ~12 and −18 °C on the heating and cooling regimes, respectively. This means a considerable shift to lower temperatures of the transition temperatures concerning the P/Q transformations previously described for the NaNbO3 material. At an intermediate frequency of 10 kHz, maximum permittivity and tangent loss values of ε' = 1250 and tgδ = 2 were obtained on heating, whereas lower values of ε' = 65 and tgδ = 0.04 were displayed on cooling regime. These anomalies were interpreted in terms of ferrolectric-antiferroelectric-paralectric phase-transitions implying a PTCR behavior within certain temperature range. This response, observed in this complex material for the first time, has interesting implications for the possible application of NN ceramics in sensing and dielectric materials fields.