The sensing spatial resolution and signal-to-noise ratio (SNR) of Raman distributed optical fiber sensors are limited by the pulse width and weak Raman scattering signals. Notably, the sensing spatial resolution cannot exceed the order of meters at several kilometers sensing distances. To break through this physical bottleneck, a novel, to our knowledge, Raman scattering model based on paired-pulse sensing is constructed. The fundamental origins of the observed limited spatial resolution of conventional schemes are analyzed, and a chaotic asymmetric paired-pulse correlation-enhanced scheme for Raman distributed fiber-optic sensing is proposed and experimentally demonstrated. The proposed scheme uses a chaotic asymmetric paired-pulse as the sensing signal and extracts the light intensity information of each data point of the sensing fiber, which carries the random undulation characteristics of chaotic time series, based on the time-domain differential reconstruction method. This scheme overcomes the pulse width limitation of spatial resolution via correlation and demodulation, enhances the correlation characteristics between the temperature-modulated Raman scattered light field and detection signal, and improves the SNR. Finally, a sensing performance of 10 km, a spatial resolution of 30 cm, and an SNR of 6.67 dB are realized in the experiment. This scheme provides a new research idea for a high-performance Raman distributed optical fiber sensing system.