This work reports for the first time the study of the physical and photoelectrochemical properties of KZn2 (HPO4) PO4 nanopowder, prepared by hydrothermal route at 453K. The as-synthesized compound crystallizes in a triclinic system (space group: P1) with the lattice constants: a=5.2060(2)angstrom, b=8.8524(3)angstrom, c=9.4039(3)angstrom, =96.9810(10)degrees, =101.7410(10)degrees, =106.8130(10)degrees and a crystallite size of 90nm. The observed direct optical transition of 2.88eV is due to O2-: 2pZn(2+): 4s charge transfer; a further indirect transition at 5.80eV is noticed. The electrical conductivity follows an exponential type law: sigma=sigma(o) exp (-0.08eV/kT) in the temperature range (385-500K), with an electronic hopping through mixed valences, while the negative thermo-power indicates n-type behavior. The capacitance measurement at pH7 gives a flat band potential of -0.13 V-SCE for the conduction band, which derives from Zn2+: 4s orbital and a donor density of 3.18x10(19)cm(-3). The electrochemical impedance spectroscopy shows the predominance of the faradic charge transfer. In order to support the photoelectrochemical results, the photocatalytic degradation of rhodamine B (RhB) in the presence of KZn2(HPO4)PO4, under solar light, is conducted. The results indicate 40% conversion after 300min of irradiation time. A degradation mechanism is proposed to explain the mineralization. The photocatalytic RhB degradation obeys to a second-order kinetic model with a rate constant of 1.48x10(-3)mol(-1)Lmin(-1).