Abstract: We investigated the crystallization of ferrihydrite prepared by hydrolysis of Fe(NO3)3 solutions containing phosphate. Crystallization was studied at different pH (3–9), temperatures (298, 323, and 373 K), and initial P/Fe atomic ratios for periods to 730 d. Generally, crystallization was inhibited or only poorly crystallized lepidocrocite was formed at P/Fe > 2.5%. Phosphate favored the formation of hematite over goethite at all temperatures for most of the pH and P/Fe ranges investigated. This result is consistent with a model in which phosphate acts as a template for hematite formation, in analogy with other anions, such as oxalate. However, goethite was preferentially formed at alkaline pH and P/Fe > 1%, probably because high phosphate concentration resulted in a large increase in the negative charge of the ferrihydrite particles. This resulted in turn in less aggregation, a process that is known to precede dehydration to hematite. Phosphate greatly influenced the morphology of hematite and goethite. Hematite was often ellipsoidal or spindle-shaped. Twinned goethite crystals with a hematite core were formed at alkaline pH at P/Fe > 1%. Both hematite and goethite particles incorporated phosphate in an occluded form not desorbable by repeated alkali treatments.