Ferriphoxite, [(NH4)2K(H2O)][Fe3+(HPO4)2(C2O4)], and carboferriphoxite, [(NH4)K(H2CO3)][Fe3+(HPO4)(H2PO4)(C2O4)], are new mineral species from the Rowley mine, Maricopa County, Arizona, USA. They occur with antipinite, aphthitalite, baryte, fluorite, hematite and quartz in an unusual bat-guano-related, post-mining assemblage. Ferriphoxite occurs as rectangular blades, up to ∼0.1 mm in length, typically forming sprays. Carboferriphoxite occurs as needles or blades, up to ∼0.2 mm in length, typically forming fan- and bowtie-like sprays. Both species are colourless with white streak, vitreous lustre, ∼2 Mohs hardness, brittle tenacity and splintery fracture. Ferriphoxite has three good cleavages ({100}, {010} and {001}) and carboferriphoxite has two good cleavages (probably {100} and {001}). Both species have a measured density of 2.14(2) g·cm–3. Ferriphoxite is biaxial (+) with α = 1.524(3), β = 1.560(3), γ = 1.608(3) and 2Vmeas. = 83.9(4)°. Carboferriphoxite is biaxial (+) with α = 1.525(3), β = 1.555(calc), γ = 1.630(3) and 2Vmeas. = 67(1)°. Electron probe microanalysis gave {[(NH4)2.13K0.87]Σ3.00(H2O)} {(Fe3+0.95Al0.05)Σ1.00(HPO4)2(C2O4)} for ferriphoxite and {[(NH4)1.12K0.88]Σ2.00(H2CO3)} {(Fe3+0.78Al0.22)Σ1.00(HPO4)(H2PO4)(C2O4)} for carboferriphoxite. Ferriphoxite is monoclinic, P21/c, with a = 11.389(5), b = 6.352(3), c = 18.716(9), β = 102.887(9)°, V = 1319.8(11) Å3 and Z = 4. Carboferriphoxite is triclinic, P
$\bar 1$, with a = 6.4405(3), b = 9.399(5), c = 11.839(6) Å, α = 95.763(10), β = 92.314(10), γ = 100.665(8)°, V = 695.6(6) Å3 and Z = 2. The structures of ferriphoxite (R1 = 0.0678 for 1850 I > 2σI reflections) and carboferriphoxite (R1 = 0.0427 for 3602 I > 2σI reflections) both contain double-strand chains of corner-sharing Fe3+O6 octahedra and PO3(OH) tetrahedra. The chain in ferriphoxite is decorated by PO3OH tetrahedra and C2O4 groups and that in carboferriphoxite is decorated by PO2(OH)2 tetrahedra and C2O4 groups. The interstitial units in both structures contain K+ and NH4+ cations along with a H2O group in ferriphoxite and an H2CO3 group in carboferriphoxite.