Results from the analysis of aqueous and solid-phase V speciation within samples collected from the Hazeltine Creek catchment affected by the August 2014 Mount Polley mine tailings dam failure in British Columbia, Canada, are presented. Electron microprobe and X-ray absorption near-edge structure (XANES) analysis found that V is present as V3+ substituted into magnetite and V3+ and V4+ substituted into titanite, both of which occur in the spilled Mount Polley tailings. Secondary Fe oxyhydroxides forming in inflow waters and on creek beds have V K-edge XANES spectra exhibiting E1/2 positions and pre-edge features consistent with the presence of V5+ species, suggesting sorption of this species on these secondary phases. PHREEQC modeling suggests that the stream waters mostly contain V5+ and the inflow and pore waters contain a mixture of V3+ and V5+. These data, and stream, inflow, and pore water chemical data, suggest that dissolution of V(III)-bearing magnetite, V(III)- and V(IV)-bearing titanite, V(V)-bearing Fe(-Al-Si-Mn) oxhydroxides, and V-bearing Al(OH)3 and/or clay minerals may have occurred. In the circumneutral pH environment of Hazeltine Creek, elevated V concentrations are likely naturally attenuated by formation of V(V)-bearing secondary Fe oxyhydroxide, Al(OH)3, or clay mineral colloids, suggesting that the V is not bioavailable. A conceptual model describing the origin and fate of V in Hazeltine Creek that is applicable to other river systems is presented.