Matioliite, ideally NaMgAl5(PO4)4(OH)6·2H2O, occurs as a secondary hydrothermal mineral in the Gentil mine granite pegmatite, Mendes Pimentel Co., Minas Gerais, Brazil. Some crystals are zoned to more Fe-rich compositions with an Fe2+:Mg ratio of approximately 1:1, corresponding to an intermediate member of the burangaite-matioliite solid-solution series. Matioliite is intimately associated with fluorapatite, crandallite, and zoned gormanite-souzalite cystals. The mineral forms prismatic to tabular crystals, up to 1 mm long. Matioliite is transparent and displays a vitreous luster; it is blue to colorless with a white streak. It is non-fluorescent. Mohs hardness is about 5. Calculated density is 2.948 g/cm3. Matioliite is biaxial negative, ηα = 1.597(2), ηβ = 1.627(2), ηγ = 1.632(1) (white light), 2V (meas.) = 43(2)°, 2V (calc.) = 44°, dispersion r > v, orientation X = b, Z ^ c = 6°. Pleochroism is Y > X > Z, X = light blue to colorless, Y = blue, Z = colorless. The empirical formula is (Na0.94Ca0.01)∑0.95(Mg0.88Fe0.112+Mn0.01)∑1.00(Al4.84Fe0.133+)∑4.97(PO4)4.03(OH)5.76·2H2O. The mineral is monoclinic, space group C2/c, a = 25.075(1) Å, b = 5.0470(3) Å, c = 13.4370(7) Å, β= 110.97(3)°, V = 1587.9(4) Å3, Z = 4. Crystal-structure determination was carried out and showed it is isostructural with burangaite, dufrénite, and natrodufrénite. Both the description and the name were approved by the CNMMN-IMA (Nomenclature Proposal 2005-011). The “magnesium analog of burangaite” described from the Gold Quarry mine, Carlin-trend, Eureka County, Nevada; “burangaite” from Hochgosch, Millstätter See-Rücken, Kärnten, Austria; and “burangaite” described from Córrego Pomarolli, Linópolis, Divino das Laranjeiras, Minas Gerais, Brazil, are probably matioliite.