Understanding the groundwater storage and release (S-Q) process and its contribution to river flows is essential for different hydrological applications, especially in periods of water scarcity. The S-Q process can be characterized based on recession parameter b, which is the slope of the power–law relationship −dQ/dt = aQb of the recession flow analysis, where recession parameter b represents the linearity of the S-Q process. In various studies, it has been found that this parameter can present high variability, which has been associated with the approach or spatial variability of basin characteristics. However, the variability of parameter b and its relationship with geology and the behavior of groundwater storage over time (evolution over time) have not been sufficiently studied. The objective of this study is to analyze the variability of recession parameter b and its relationship with geological and morphological characteristics and climate variability at different time scales. To this end, 72 drainage basins located in south central Chile were examined via recession flow analysis, considering five different time scales (5 years, 10 years, 15 years, 20 years, and 25 years). In addition, to analyze spatial variability patterns and generate groups of basins with similar characteristics, a cluster analysis was carried out. Clusters were obtained using the principal component analysis (PCA) and K-means methods. The results show that in wet periods, the slope of recession parameter b tends to increase (fast drainage process), while in dry periods, the recession slope tends to decrease (slow drainage processes). In general, the results suggest that the variability of recession coefficient b indicates changes in S-Q behavior; therefore, it could be used as an indicator of the sensitivity of a basin to climate variability.