The El Nino Southern Oscillation (ENSO) is a semi-periodic fluctuation in sea surface temperature (SST) over the tropical central and eastern Pacific Ocean that influences interannual variability in regional hydrology across the world through long-range dependence or teleconnections. Recent research has demonstrated the value of Deep Learning (DL) methods for improving ENSO prediction as well as Complex Networks (CN) for understanding teleconnections. However, gaps in predictive understanding of ENSO-driven river flows include the black box nature of DL, the use of simple ENSO indices to describe a complex phenomenon and translating DL-based ENSO predictions to river flow predictions. Here we show that eXplainable DL (XDL) methods, based on saliency maps, can extract interpretable predictive information contained in global SST and discover novel SST information regions and dependence structures relevant for river flows which, in tandem with climate network constructions, enable improved predictive understanding. Our results reveal additional information content in global SST beyond ENSO indices, develop new understanding of how SSTs influence river flows, and generate improved river flow predictions with uncertainties. Observations, reanalysis data, and earth system model simulations are used to demonstrate the value of the XDL-CN based methods for future interannual and decadal scale climate projections.