A new series of lead-based monophosphate tungsten bronzes (MPTB h ), Pb x (PO 2 ) 4 (WO 3 ) 2m , was isolated for 64m410 and characterized by X-ray diffraction, electron microscopy, and resistivity and magnetic susceptibility measurements. The crystal structure was solved for m ؍ 7 from three-dimensional single-crystal X-ray data [Pb 0.66 P 4 W 14 O 50 : triclinic, A1 , a ؍ 6.6015(3) A s , b )4(6513.5؍ A s , c )2(930.72؍ A s , ,°)6(802.09؍ ؍ 96.757(5)°, ؍ 89.867(5)°, Z ؍ 1, final R ؍ 2.16% for 4462 independent reflections with I > 3.0 (I)]. Lead atoms are distributed in cages bounded by 18 oxygen atoms, in a part that favors a PO 4 tetrahedron neighbor rather than a WO 6 octahedron neighbor. Consequently, Pb atoms exhibit an (3؉5) eightfold coordination that takes into account the 6s 2 lone-pair stereoactivity. Resistivity measurements performed on oriented single crystals reveal quasi-two-dimensional metallic behavior for the entire temperature range investigated, 4.2 to 300 K. Magnetic susceptibility data indicate Pauli paramagnetic behavior. The results are compared with those of alkaline-based counterparts, A x (PO 2 ) 4 (WO 3 ) 2m (A ؍ Na, K).