Arsenate (AsO43−) is a common species in oxidizing aquatic systems and hydrothermal fluids, and its solubility and partitioning into different mineral phases are determined by the nature of AsO43− coordination, solution pH, type of soluble cations, and H2O structure at the mineral-fluid interfaces. While the vibrational spectroscopy has been widely used in examining the AsO43− coordination chemistry, insufficient knowledge on the correlation of AsO43− molecular structure and its vibrational spectra impeded the complete spectral interpretation. In this paper, we evaluated the vibrational spectroscopy of AsO43− in solutions, crystals, and sorbed on mineral surfaces using theoretical (semiempirical, for aqueous species) and experimental studies, with emphasis on the protonation, hydration, and metal complexation influence on the As-O symmetric stretching vibrations. Theoretical predictions are in excellent agreement with the experimental studies and helped in the evaluation of vibrational modes of several arsenate-complexes and in the interpretation of experimental spectra. These vibrational spectroscopic studies (IR, Raman) suggest that the symmetry of AsO43− polyhedron is strongly distorted, and its As-O vibrations are affected by protonation and the relative influence on AsO43− structure decreases in the order: H+ ≫ cation ≥ H2O. For all AsO43−complexes, the As-OX symmetric stretching (X = metal, H+, H2O; ≤820 cm−1) shifted to lower wavenumbers when compared to that of uncomplexed AsO43−. In addition, the As-OH symmetric stretching of protonated arsenates in aqueous solutions shift to higher energies with increasing protonation (<720, <770, <790 cm−1 for HAsO42−, H2AsO4−, and H3AsO40, respectively). The protonated arsenates in crystalline solids show the same trend with little variation in As-OH symmetric stretching vibrations. Since metal complexation of protonated AsO43− does not influence the As-OH vibrations significantly, deducing symmetry information from their vibrational spectra is difficult. However, for metal unprotonated-AsO43− complexes, the shifts in As-OM (M = metal) vibrations are influenced only by the nature of complexing cation and the type of coordination, and hence the AsO43− coordination environment can be interpreted directly from the splitting of As-O degenerate vibrations and relative shifts in the As-OM modes. This information is critical in evaluating the structure of AsO43− sorption complexes at the solid-water interfaces. The vibrational spectra of other tetrahedral oxoanions are expected to be along similar lines.