Three new alkaline earth metal based metal-organic frameworks (MOFs), namely M-BPTC (M = Mg, Sr, Ba), have been synthesized by using BPTC (2,2',6,6'-tetracarboxybiphenyl) as ligand under hydrothermal conditions. These MOFs exhibit interesting structural diversity, variable chemical and thermal stability, as well as proton conductivity. Mg-BPTC with the formula {[Mg(BPTC)(0.5)(H2O)(3)]5H(2)O}(n) consists of BPTC4- extended metal layers, and novel highly ordered infinite tape-like structures of cyclic water octamers reside interlayer. Three-dimensional porous {[Sr-2(BPTC)(H2O)(6)]H2O}(n) (Sr-BPTC) features inorganic Sr-O chains ((IO2)-O-1) and open hydrophilic channels where water heptamers and carboxyl oxygen atoms conspire to form H-bond networks, whereas 3D {[Ba-6(BPTC)(3)(H2O)(6)]11H(2)O}(n) (Ba-BPTC) shows Ba-O inorganic layer ((IO1)-O-2) and 1D channels incorporating large water 14-mers and 18-mers. M-BPTC (M = Mg, Sr) species exhibit excellent water stability and proton conductivity due to their respective appropriate pathways for proton transporting. M-BPTC (M = Sr, Ba) structures are highly thermally stable due to the presence of the inorganic connectivity. The present results suggest that M-BPTC (M = Mg, Sr) are promising materials for proton conduction and provide insight into the hydrogen bonding motif.