Binary melts were prepared from a-picolinium chloride (α-PicHCl) and lithium chloride. Densities, electrical conductivities, viscosities and glass transition temperatures were determined. Transport properties data were studied by VTF equation and fragility concept applied. Both, Tg data and T0 parameters indicate the existence of a broad maximum around X(LiCl) = 0.25 due to a low value of configurational entropy. Viscosity and electrical conductivity support the formation of [LiCl4][α-picH]3 complex species. Also, those values of transport and cohesive properties were compared with values of acidic l-methyl-3-ethylimidazolium chloride, aluminium chloride and lithium chloride melt systems.