Highly fluorinated organic or organometallic solid compounds can be made to dissolve in liquid hydrocarbons by the application of 20-70 bar of CO2 gas, Subsequently releasing the gas causes the compounds to precipitate or crystallize, giving quantitative recovery of the solid. The resulting crystals can be of sufficient quality for single-crystal X-ray crystallography; the structures of Rh-2(O2CCF2CF2CF3)(4)(DMF)(2), Rh-2(O2C(CF2)(9)F)(4)(MeOH)(2), Cr(hfacac)(3), and P{C6H3(3,5-CF3)(2)}(3) have been determined from crystals grown in this manner.