Understanding the rainfall-streamflow relationship is fundamental for effective water resource planning and agricultural management in river basins. This study presents a comprehensive, sub-catchment scale analysis of the rainfall-streamflow correlation, regression and runoff coefficients for 15 sub-catchments within the Mahanadi River Basin (MRB). High-resolution gridded rainfall data from the India Meteorological Department (IMD) and observed streamflow data from the Central Water Commission (CWC) were utilised from the year 1980 to 2024 to establish the relationships. The correlation analysis revealed a strong positive linear relationship between rainfall and streamflow across the basin, with a basin-average correlation coefficient (r) of 0.78. Sub-basin wise, the lower Mahanadi River Basin (LMRB) exhibited the strongest coupling (average r = 0.83), followed by the middle Mahanadi River Basin (MMRB, average r = 0.77) and upper Mahanadi River Basin (UMRB, average r = 0.75) sub-basins. The coefficient of determination (R²) followed a similar pattern. The estimated runoff coefficients (C), representing the fraction of rainfall converted into streamflow, showed significant spatial variability, ranging from 0.13 to 0.43 across sub-catchments. The upper and middle sub-basins showed lower runoff coefficients (UMRB: 0.22, MMRB: 0.32), while the lower sub-basin demonstrated a higher runoff coefficient of 0.35. These spatial patterns are attributed to the attenuating effects of major dams and reservoirs in the upper and middle reaches, higher forest cover promoting infiltration and contrasting topography. The flatter, deltaic lower basin, influenced by cumulative flow and higher water tables, generates runoff more efficiently. These findings are critical for designing sub-basin specific water management strategies. This study provides vital quantitative insights for optimising agricultural water use and implementing climate-resilient practices across the Mahanadi basin.