Ionic liquids (ILs) have significant potential for eco-friendly extraction of uranium from aqueous solutions, which is critical for nuclear technology, fuel cycle management, and environmental protection. This study examines the impact of the adjustable hydrophobic/hydrophilic properties of ILs on the removal of uranium(VI) (UO22+) from aqueous solutions utilizing both a novel hydrophilic IL (1-butoxyethyl-1-methylmorpholinium butoxyethylphosphite - Mor1-2O4-BOEP) and 1-heptyl-1-methylmorpholinium heptylphosphite (Mor1-7-HP) as an example of a hydrophobic IL with a similar structure. The transfer mechanism of uranyl ions from water to organic or solid phases closely depends on the physicochemical properties of ILs, especially their hydrophobicity. The hydrophobic Mor1-7-HP extracts uranyl via neutral complex formation as UO2(NO3)2-(Mor1-7-HP)2. Conversely, hydrophilic Mor1-2O4-BOEP induced selective precipitation as UO2(NO3)-(BOEP), transferring uranyl to the solid phase. Optimization of the working parameters, in terms of acidity of the aqueous solution and amount of ILs used, allowed the extraction of over 98% of U(VI). The stoichiometry of the organic complex and the precipitate was determined using physicochemical techniques. These tunable H-phosphonate-based ILs have advantages over traditional solvent extraction and conventional ILs, allowing easier handling, improved selectivity, and lower environmental impact. This work advances uranium separation techniques with applications in hydrometallurgy, particularly in the treatment of wastewater and radioactive waste for sustainable uranium recovery.