The hydration structure and aqueous acetate complexation of Cr3+ ions were studied by X-ray absorption fine structure (XAFS) spectroscopy as a function of pH, concentration, acetate:Cr ratio, and age of the solution. In the perchlorate solutions, we found an octahedral hydration shell around the Cr3+ ion at 1.96 Angstrom, confirming previous results through an independent analysis. Distinct Cr-Cr correlation was observed in the Cr acetate solutions, indicating that acetate groups bridge between the metal ions in a polymer structure. Modeling of the data confirmed a cyclic trichromium complex in acetate solutions. Similar spectral features in the Fourier transform were observed at 3.0-3.5 Angstrom for both hydrated and polynuclear Cr. Comparison of the spectral content of such features in the two different cases showed that the origin of the 3.0-3.5 Angstrom structure is multiple scattering within the first O shell alone. Thus, no spectral contribution could be attributed to the outer hydration molecules in data for hydrated Cr3+. We also report on differences in first-shell O backscattering (or possible spectral contributions from H atoms) in the aqueous solutions relative to the crystal oxide, determined by systematic analysis of a Cr2O3 standard.