Most compounds designed for immobilization in fluorous media feature linear pony tails of the formula (CH 2) m (CF 2) n−1 CF 3 [(CH 2) m R f n ]. This paper presents a first-generation approach to compounds with branched or “split” pony tails of the formula (CH 2) l CH[(CH 2) m R f n ] 2. Allyl tri( n-butyl)tin is reacted twice with perfluorooctyl iodide (R f8I; first, photochemical, 78–81%; second, thermal with radical initiator, 71%; 13–18 g scales) to give the secondary alkyl iodide ICH(CH 2R f8) 2 ( 3). A subsequent Ni(Cl) 2(PPh 3) 2-catalyzed reaction with allyl tri( n-butyl)tin yields the branched alkene H 2CCHCH 2CH(CH 2R f8) 2 (74%). A palladium-catalyzed Heck coupling with OP( p-C 6H 4Br) 3 gives the fluorous phosphine oxide OP( p-C 6H 4CHCHCH 2CH(CH 2R f8) 2) 3 (84%), and Pd/C-catalyzed hydrogenation affords OP( p-C 6H 4(CH 2) 3CH(CH 2R f8) 2) 3 (>99%). Reduction with SiHCl 3 gives P( p-C 6H 4(CH 2) 3CH(CH 2R f8) 2) 3, which is protected as the air-stable borane adduct H 3B·P( p-C 6H 4(CH 2) 3CH(CH 2R f8) 2) 3 ( 9, 64%). The CF 3C 6F 11/toluene partition coefficient of 9 is much higher than that of the analog with p-(CH 2) 3R f8 groups (96.6:3.4 versus 37.3:62.7). The iodide 3 is unreactive towards PAr 3 at 175–250 °C. However, a CuBr-catalyzed reaction with C 6H 5MgBr gives C 6H 5CH(CH 2R f8) 2, which also exhibits a high partition coefficient (97.9:2.1).