We have developed an example of hydrocarbon detection for an Ordovician cavern carbonate reservoir in western China with a burial depth exceeding 6600 m using amplitude variation with offset (AVO) and spectral decomposition. We selected six production wells, three prolific oil wells, and three brine wells to test the hydrocarbon detection method. The three oil wells have been producing for more than three years, and the three water wells only produce brine. We performed spectral decomposition to the angle gathers and analyzed amplitude variation patterns with incidence angles for different spectral components. Specifically, we compared the time corresponding to the peak spectral amplitude for different spectral components for the oil- and brine-saturated carbonate reservoirs. The main findings are as follows: (1) Oil-saturated cavern carbonate reservoirs show decreasing peak time with increasing frequency; i.e., the high-frequency components travel faster than do the low-frequency components. The maximum time difference between the 10 and 50 Hz spectral components could reach 35 ms. In contrast, the brine-saturated carbonate reservoirs do not exhibit conspicuous variation in the peak time, (2) AVO attributes extracted from the low-frequency spectral gathers are more robust than those extracted from the original seismic gathers, (3) oil-saturated cavern carbonate reservoirs cause strong energies in the low-frequency spectral components and severe attenuation to the high-frequency spectral components at large incidence angles. In contrast, the brine-saturated carbonate reservoirs do not produce such phenomenon. Rock physics analysis for carbonate reservoirs under different saturation conditions was conducted. The synthetic gathers were generated for carbonate reservoirs under oil- and brine-saturated conditions. The spectrally decomposed synthetic gathers are in agreement with the real gathers. The results indicate that AVO analysis of spectrally decomposed prestack gathers could be used as an effective hydrocarbon detection method for carbonate reservoirs.