Narrow MW distribution perfluorocarbon end-functionalized polystyrene of the (E) (C13F27) and telechelic (T) (C7F15) with molecular weights (MWs) of about 15 k and 30 k and the corresponding isobaric polybutylmethacrylate were synthesized by a combination of ATRP and Cu (I) catalyzed click-coupling reactions. Blends of the E and T-type PS/PBMA (1/1 w/w) with nearly identical MWs of 15 and 30 kDa and RF contents were compared using TEM, AFM, DSC and optical transmittance. The 15 k blends with the same RF contents were both homogeneous as indicated by DSC data and the similar TEM and AFM morphologies but somewhat smaller sized lamellar TEM domains for the T-type blends. Much larger differences are seen for the 30 k-T and eE blends, as indicated by the relatively well defined but disordered 50-100 nm. domains of the T-30 k blend while the 30k-E blend shows a completely different morphology with ill defined micron sized domains. The AFMs of the 30k-E-blend showed similar large changes with 3e8 m sized domains while the 30 k-T blend showed domains in the 50e500 nm scale. at the seen for the 30 k-E type blend that were also more pronounced for the 30 k blends. These results are consistent with the optical transmissions and DSC data.