Two polytypes of the new oxyvanadate matrix La7O6(VO4)(3) were identified and deeply characterized. The crystal structure of the alpha-polytype was solved using a combination of precession electron diffraction and powder X-ray diffraction (XRD) techniques. It crystallizes in a monoclinic unit cell with space group P2(1), a = 13.0148(3) angstrom, b = 19.1566(5) angstrom, c = 7.0764(17) angstrom, and beta = 99.87(1)degrees. Its structure is built upon [La7O6](9+) polycationic units at the origin of a porous 3D network, evidencing rectangular channels filled by isolated VO4 tetrahedra. An in situ high-temperature XRD study highlights a number of complex phase transitions assorted with the existence of a beta-polytype also refined in a monoclinic unit cell, space group P2(1)/n, a = 13.0713(4) angstrom, b = 18.1835(6) angstrom, c = 7.1382(2) angstrom, and beta = 97.31(1)degrees. Thus, during the transitions, while the polycationic networks are almost identical, the vanadate's geometry is largely modified. The use of Eu3+ and Sm3+ at different concentrations in the host lattice is possible using solid-state techniques. The photoluminescence (PL), PL excitation (PLE) spectra, and luminescence decay times were recorded and discussed. The phosphors present an emission light, being bright and reddish orange after excitation under UV. This is mainly due to the V-O band and f-f transitions. Whatever the studied polytype, the final luminescence properties are retained during the heating/cooling process.