To reveal the influence of water accumulation in open pits on the stability of boundary coal–rock pillars, this study investigates a boundary coal–rock pillar between an underground coal mine and an adjacent open pit in western China. Coal–rock physical property tests, hydrochemical analysis, permeability tests, and theoretical calculations of water-resisting coal–rock pillars were conducted to examine seepage channel formation, physical property changes, and stability evolution under long-term water accumulation. The results show that the mechanical strength of coal and rock specimens decreases under the saturated state. The uniaxial compressive strength of rock specimens decreases by 8.75–50.64%, while that of No.2−2 and No.3−1 coal specimens decreases by 17.72% and 25.01%, respectively. The tensile strength decreases by 24.59–59.11%, and the shear strength decreases by 4.36–45.96%. The hydraulic conductivity of intact specimens is mostly 10−4~10−3 m/d, whereas that of fractured specimens increases to 10−3~10−2 m/d. The calculated width of water-resisting coal pillars increases by 19.7~21.9% under long-term water accumulation. Long-term water accumulation in the open pit changes the external hydraulic boundary of the boundary coal–rock pillar, allowing water to migrate inward along bedding planes, joints, primary fractures, mining-induced fractures, and coal seam pores. This process promotes the connection of pre-existing pore–fracture structures and seepage channel formation, weakens particle cementation and structural-plane shear resistance, and reduces the structural integrity, bearing capacity, and water-resisting capacity of the coal–rock pillar. Therefore, the stability deterioration of boundary coal–rock pillars is a continuous process involving channel formation, sustained seepage, strength degradation, enhanced pore–fracture connectivity, permeability enhancement, and further stability reduction.