A kind of new conjugated rigid-rod polymer poly(9,9-dioctyl fluorenol benzobisoxazole) (PBOF) containing an fluorene and benzobisoxazole structure was prepared by the 4,6-diamino-1,3-benzenediol dihydrochloride (DAR) and 9,9-dioctyl fluorene. The polymer was characterized by the elemental analysis, (HNMR)-H-1, FTIR, thermogravimetric analysis (TGA) and photoluminescence (PL) spectra. The results indicated that the thermal stability of polymer was much lower than that of well-known poly(p-phenyl benzobisoxazole) (PBO). Unlike PBO, PBOF was readily soluble at room temperature in DMSO and NMP and even partly dissolved in m-cresol and CHCl3 due to the introduction of alkyl groups. The absorption and photoluminescence spectra of the polymer were also studied. The protonated PBOF in dilute methanesulfonic acid solutions exhibits a blue emission with a peak at 468 nm. In contrast with that of PBO, the maximal emissions spectra and absorption spectra of PBOF red-shifted due to the introduction of the fluorene group which enhanced effective conjugation of polymer structure unit.