A solvothermal reaction of ZnO, HCl, H3PO4, and N,N′(3-bisaminopropyl)-1,2-ethylenediamine (BAPEN) in diethyleneglycol at 160°C yields a new zinc chlorophosphate, [C8N4H26][Zn3Cl(HPO4)3(PO4)], I. The structure comprises ZnO4, ZnO3Cl, HPO4 and PO4 tetrahedral units connected through their vertices giving rise to a layered structure with 10-membered apertures. The position of the Zn and P atoms gives rise to double-four ring like building unit with one Zn missing. The fully protonated amine molecules occupy the inter-lamellar region and interacts with the framework through N–H⋯O hydrogen bonds. Crystal data: M=792.85, orthorhombic, space group=Pca21 (no. 29), a=9.8410(2), b=15.0912(2), c=16.1220(4) Å, V=2394.32(8) Å3, Z=4, ρcalc=2.199 g cm−3, μ(MoKα)=3.443 mm−1, R1=0.0520, wR2=0.1256 and S=1.054.