An organometallic non-aqueous route to zinc phosphonates and to their intercalates has been studied. Various phosphonic acids react with dimethylzinc in THF media to afford the corresponding layered zinc phosphonates Zn(O 3 PR 1 ) (R 1 = Me, Ph, 2- and 3-thienyl, thiophen-3-ylmethyl) with evolution of methane. The presence of a primary n-alkylamine in the reaction mixture allows the one-pot formation of 2D-layered intercalated phases of general formula Zn(O 3 PR 1 )·RNH 2 [R 2 = Bu n , Pen n (= n-pentyl)] whereas a more bulky amine such as cyclohexylamine (Hex c NH 2 ) lead to the formation of 1D polymeric chains of formula Zn(O 3 PPh)·2Hex c NH 2 .