Four fluorine-containing X-branched oligophenylenes, X-OPP(5)-Fn, n = 1,2,3 and X-OPP(5)-CF3, have been synthesized and studied as potential hole-blocking materials. These molecular materials exhibit a low HOMO energy level (ca. 6.5 eV) and a large energy gap (ca. 3.5 eV), indicating that they can be employed as effective hole-blockers in blue-emitting organic EL devices. Four-layer organic EL devices consisting of CuPc as a hole injection layer, α-NPD as a hole-transporting and emitting material, X-OPP(5)-Fn or X-OPP(5)-CF3 as a hole-blocker, and Alq3 as an electron-transporter sandwiched between indium tin oxide (ITO) and LiF/Al electrodes were fabricated, and their performance was examined and compared with the widely used hole-blocker bathocuproine (BCP), the non-fluorine-containing X-branched analogue X-OPP(5)-H and the X-branched analogue with one less phenyl ring, X-OPP(3)-F2. The preliminary results show that these new molecular materials, especially X-OPP(5)-F2, are excellent hole-blockers for blue-emitting organic EL devices.