A new 2D hydrogen-bonded supramolecular framework based on acyclic water tetramer clusters and tetraprotonated triethylenetetramine (denoted by H4TETA) molecules is formed in a new sodium molybdenum(V) phosphate compound, [H4TETA]4NaMo12V(OH)6(HPO4)(PO4)7O24·11H2O (1), which is hydrothermally prepared and characterized thoroughly. Single crystal X-ray diffraction analysis reveals that the 2D supramolecular framework is composed of unique kind of “hexagon” pores each of which is formed by the connection of alternate acyclic water tetramer cluster and H4TETA molecules via hydrogen-bonding interactions. In between the 2D frameworks the NaMo12V(OH)6(HPO4)(PO4)7O2416- anions partially infix sideling into the hexagon pores through H-bonding interaction with standing style anions sandwiched in one interlayer and the lying style ones in another interlayer alternately, and consequently a 3D sandwich type supramolecular entity is resulted. Moreover, the electrochemical properties and preliminary catalytic properties toward rhodamine B degradation of the compound 1 are also investigated.