Investigating the correlation between ecosystem services and the alignment of water and land resources facilitates the sustainable development of ecological resources. The Huaihe River Basin was selected as the research subject, employing the equivalent factor approach to quantify the ecosystem service value (ESV) and assess the matching coefficient of water and land resources. The coupled coordination degree model was employed to investigate the synergistic development trend between the two entities. The Dagum Gini coefficient was employed to analyze the origins of regional variation in coordination degree. The results show that: (1) The ESV has risen by 12.294 billion yuan. The average ESV of the land is elevated in the east and diminished in the west. (2) The matching coefficient of water and land resources exhibits an increasing tendency. The transformation from 2010 to 2020 is more favorable in the interior compared to the periphery and more advantageous in the north than in the south. (3) The degree of coupling coordination exhibits a declining trend and a distribution pattern characterized by “higher in the east and lower in the west”. The disparity in the level of coupling coordination among regions is progressively widening. The contribution rate of inter-regional disparities is 75.36%.