Lithium dihydrogen phosphate (LiH2PO4) powder was purchased from Aldrich Chemical Co. Fromthe scanning electron microscope (SEM) observation, these polycrystals have dimensions in the range of 25-250µm. The electrical conductivity was measured at a measuring frequency of 1 kHz on heating polycrystallinelithium dihydrogen phosphate (LiH2PO4) from room temperature to 493 K. Two anomalies appeared at 451K (Tp1) and 469 K (Tp2). The electrical conductivity reached the magnitude of the superprotonic phases: 3×10-2Ω-1cm-1 at 451 K (Tp1) and 1.2×10Ω-1cm-1 at 469 K (Tp2). It is uncertain whether the superprotonic phasetransformations are due to polymorphic transitions in the bulk, surface transitions, or chemical reactions(thermal decomposition) at the surface. Considering several previous thermal studies (differential scanningcalorimetry and thermogravimetry), our experimental results seem to be related to the last case: chemicalreactions (thermal decomposition) at the surface with the progressive solid-state polymerization.