Three　ortho-,　meta-,　and　para-linked　polymers　derived　from　9,9-dioctylfluorene　(FO)　and　dimethoxyl-biphenyl　(DMBP)　were　designed　and　synthesized　via　catalyst-transfer　Suzuki　coupling　polymerization　with　palladium(0)　catalyst　as　initiator.　Compared　to　PFO,　the　conjugated　polymers　of　PFO-o-DMBP,　PFO-m-DMBP,　and　PFO-p-DMBP　displayed　a　significantly　blued-shifted　absorption　and　emission　spectra　with　the　change　of　the　connecting　site　from　ortho-,　meta-　to　para-position,　and　the　varying　degrees　were　ascribed　to　the　different　types　of　steric　hindrance　of　ortho-,　meta-,　and　para-linkage,　which　partly　hinder　the　intermonomer　rotation　of　the　polymer　backbone,　giving　rise　to　molecular　configuration　from　linear,　zigzag　to　intertwined　structure,　and　resulting　in　shortened　conjugation　length.　The　optical　bandgap　calculated　from　the　onset　of　absorption　spectra　of　the　three　polymers　in　solid　film　are　all　wider　than　that　of　the　PFO,　indicating　that　the　incorporating　of　dimethoxyl-biphenyl　increased　the　chain-twisting　hindrance　and　influenced　the　molecular　conformation　of　the　copolymer.　Systematical　investigation　of　electrochemical　and　photophysical　properties　of　the　conjugated　polymers　suggests　that　the　incorporation　of　dimethoxyl-biphenyl　via　ortho-,　meta-,　and　para-linkage　is　an　efficient　and　economic　way　to　modify　the　properties　of　polyfluorenes.　©　2020　Society　of　Photo-Optical　Instrumentation　Engineers　(SPIE).