This paper describes the synthesis and characterization of γ‐zirconium phosphate‐phosphonates based on chiral N‐phosphonomethyl‐L‐proline [(−)‐HO3PCH2NHC4H7CO2H; H3PMP] from L‐proline, and N‐phosphonomethyl‐1,3‐thiazolidine‐4‐carboxylic acid [(−)‐HO3PCH2NHCH2SC2H3CO2H; H3PMTA] from L‐cysteine. Two compounds formulated as [Zr(PO4)(H2PO4)0.53(H2PMP)0.47·2.0H2O] [γ‐ZrPMP (1)] and [Zr(PO4)(H2PO4)0.50(H2PMT)0.50·1.6H2O] [γ‐ZrPMT (2)] were obtained by topotactic reaction of H3PMP and H3PMTA, respectively, with γ‐ZrP in the presence of water/acetone. They possess intercalation capabilities and optical activities. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)