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A velocity-selective spectroscopy technique for studying the spectra of Rydberg gases is presented.This method provides high-resolution spectrum measurements.We present experimental results for a ladder system 6S 1/2 → 6P3/2 → nS(D) electromagnetically-induced transparency involving highly-excited Rydberg states.Based on a radio-frequency modulation technique,we measure the hyperfine structure splitting of intermediate states and the fine structure splitting of Rydberg states in a room temperature 133Cs vapor cell.The experimental data and theoretical predictions show excellent agreement.