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Abstract Macroion‐counterion interaction is essential for regulating the solution behaviors of hydrophilic macroions, as simple models for polyelectrolytes. Here, we explore the interaction between uranyl peroxide molecular cluster Li₆₈K₁₂(OH)₂₀[UO₂(O₂)OH]₆₀(U₆₀) and multivalent counterions. Different from interaction with monovalent counterions that shows a simple one‐step process, isothermal titration calorimetry, combined with light/X‐ray scattering measurements and electron microscopy, confirm a two‐step process for their interaction with multivalent counterions: an ion‐pairing betweenU₆₀and the counterion with partial breakage of hydration shells followed by strongU₆₀‐U₆₀attraction, leading to the formation of large nanosheets with severe breakage and reconstruction of hydration shells. The detailed studies on macroion‐counterion interaction can be nicely correlated to the microscopic (self‐assembly) and macroscopic (gelation or phase separation) phase transitions in the diluteU₆₀aqueous solutions induced by multivalent counterions.