The Madeira deposit (Sn, Nb, Ta) at Pitinga, Amazonia, in Brazil, is associated with the albite-enriched facies of the A-type Madeira granite (~1,820 Ma). Fluorine (cryolite), Y, REE, Li, Zr, and Th are potential by-products of the disseminated ore. We studied the xenotime from the core albite-enriched (CAG), transitional albite-enriched granite (TAG) and pegmatitic albite-enriched granite (PAG). In all these rocks, xenotime is magmatic, has high HREE contents (0.37 to 0.54 atoms per formula unit; LREE are not detected), and low U, Th and Ca content. The CAG xenotime is the richest in REE, followed by that in the PAG and TAG units. Fluorine was detected in all xenotime crystals from CAG (up to 5.10%) and from PAG (up to 1.40%) and in most crystals from TAG (up to 0.68%). Where the xenotime is richer in F, the Na and Si increase, the P, Ca, and the effectiveness of a thorite-type substitution decrease. Fluorine controls the ratio REE/Y; the richer the xenotime in F, the richer it is in REE, in particular Er and Yb. The cell parameters a and c are significantly shortened in F-rich xenotime. There is no evidence of OH in the structure. We contend that fluorine substitutes for O to form PO3F tetrahedra, as in bobdownsite. The formation of the PO3F tetrahedra in the xenotime accounts well for the compatibility between the crystallographic characteristics and the chemical composition.