The triethylene glycol and tripropylene glycol derivatives terminated with the CO2-philic phosphoryl groups, named 2-(2-(2-((2-ethylhexoxy(methoxy)phosphoryl)oxy)-ethoxy)ethoxy)ethyl 2-ethylhexyl methyl phosphate (EG3EH) and 2-(2-(2-((2-ethylhexoxy(methoxy)phosphoryl)oxy)propoxy)-propoxy)propyl 2-ethylhexyl methyl phosphate (PG3EH), were synthesized and characterized. The solubilities of EG3EH and PG3EH in scCO(2) were determined by a static method at temperatures from (313 to 333) K and over a pressure range of (10 to 19) MPa. The values calculated by the Bartle semiempirical model exhibited good agreement with the experimental data.