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The roméite-group is part of the pyrochlore-supergroup and comprises cubic oxides of A2B2X6Y formula in which Sb5+ predominates in the B-site. The A and Y main occupants determine different minerals in the group and are important for the discovery of new mineral species. Two different roméite-group mineral samples were analysed by electron microprobe analysis (EMPA), Raman spectroscopy and single-crystal X-ray diffraction (XRD). The first sample is from Prabornaz Mine (locality of the original roméite), Saint Marcel, Valle d’Aosta, Italy, whereas the other one occurs in Kalugeri Hill, Babuna Valley, Jakupica Mountains, Nezilovo, Veles, Macedonia. Sample 1 was identified as fluorcalcioroméite, and sample 2 as hydroxycalcioroméite. Both samples belong to the cubic crystal system, space group Fd3¯m, Z = 8, where a = 10.2881(13) Å, V = 1088.9(4) Å3 for sample 1, and a = 10.2970(13) Å, V = 1091.8(4) Å3 for sample 2. The crystal structure refinements converged to (1) R1 = 0.016, wR2 = 0.042; and (2) R1 = 0.023, wR2 = 0.049. Bond-valence calculations validated the crystal structure refinements determining the correct valences at each crystallographic site. Discrepancies observed in the Sb5+ bond-valence calculations were solved with the use of the proper bond valence parameters. The resulting structural formulas are (Ca1.29Na0.55□0.11Pb0.05)Σ=2.00(Sb1.71Ti0.29)Σ=2.00[O5.73(OH)0.27]Σ=6.00[F0.77O0.21(OH)0.02]Σ=1.00 for sample 1, and (Ca1.30Ce0.51□0.19)Σ=2.00(Sb1.08Ti0.92)Σ=2.00O6.00[(OH)0.61O0.21F0.18]Σ=1.00 for sample 2. The Raman spectra of the samples exhibited the characteristic bands of roméite-group minerals, the most evident corresponding to the Sb-O stretching at around 510 cm−1.