The thermonnorphic fluorous phosphines P((CH2)(m)(CF2)(7)CF3)(3) (m = 2, 1a; m = 3, 1b) exhibit ca. 600-fold solubility increases in n-octane between -20 (1a = 0.104 mM) and 80 degreesC (63.4 mM) and 1500-fold solubility increases between -20 and 100 degreesC (151 mM). They catalyze conjugate additions of alcohols to methyl propiolate under homogeneous conditions in n-octane at 65 degreesC and can be recovered by simple cooling and precipitation and used again. This avoids the use of fluorous solvents during the reaction or workup, which are expensive and can leach in small amounts. Teflon shavings can be used to mechanically facilitate recycling, and P-31 NMR analyses indicate >97% phosphorus recovery (85.2% 1a, 12.2% other). F-19 NMR analyses show that 2.3% of the (CF2)(7)CF3 moieties of la leach, in some form, into the n-octane (value normalized to phosphorus). 1a similarly catalyzes additions in the absence of solvent. Yield data match or exceed those of reactions conducted under fluorous/organic liquid/liquid biphase conditions. The extra methylene groups render 1b more nucleophilic than la and, thus, a more active catalyst. The temperature dependence of the solubility of 1 a is measured in additional solvents and compared to that of the nonfluorous phosphine PPh3.