We have developed a highly precise method for the determination of ferrous iron (Fe²⁺) in silicate rocks. Our new method is based on Wilson’s procedure (1955) in which surplus V⁵⁺ is used to oxidize Fe²⁺ into Fe³⁺ while equivalently reducing V⁵⁺ into V⁴⁺. Because V⁴⁺ is more resistant to atmospheric oxidation than Fe²⁺, Fe²⁺ in the sample can be determined by measuring unreacted V⁵⁺ by adding excess Fe²⁺ after sample decomposition and then titrating the unreacted Fe²⁺ with Cr⁶⁺. With our method, which involves conditioning the sample solution with 5 M H₂SO₄ in a relatively small beaker (7 mL), the oxidation of Fe²⁺ or V⁴⁺ that leads to erroneous results can be completely avoided, even in 100-h sample decompositions at 100°C. We have measured the concentration of FeO in 15 standard silicate rock powders provided by the Geological Survey of Japan (GSJ). Analytical reproducibility was better than 0.5% (1σ) for all but those samples that had small amounts of Fe²⁺ ( < 1.5 wt.% of FeO). Fourteen of these samples gave FeO contents significantly higher than the GSJ reference values. This likely indicates that the GSJ reference values, obtained by compiling previously published data, contain a large number of poor-quality data obtained by methods with lower recovery of Fe²⁺ caused by oxidation or insufficient sample decomposition during analyses. To achieve accurate determinations of Fe²⁺ in our method, several factors besides the oxidation must be considered, including: (1) long-term variations in the concentration of Fe²⁺ solution must be corrected; (2) excess use of the indicator must be avoided; and (3) the formation of inert FeF⁺ complex must be avoided during titration when using boric acid as a masking agent.