Data showing significant time resolution limited “step” capture of electrons following ~7 ps resolution pulse radiolysis in a series of different length and different concentration conjugated polyfluorene polymers in tetrahydrofuran (THF) is presented. At the highest concentration, ~48 mM in repeat units for lengths from 20-133 fluorenes, ~30% of the electrons formed during pulse-radiolysis were captured in the step, with a constant efficiency per repeat unit. Step capture per repeat unit (q=6.9 M-1) is 60% of the pre-solvated electron capture efficiency previously reported for biphenyl in THF, giving capture per polymer molecule 12-80 times larger than biphenyl at the same concentration. This increase in capture efficiency is large compared to the rate constant per repeat unit for diffusion limited electron attachment to the same molecules, which is 13% of that of a single unit of fluorene. Plausible mechanisms of this fast capture are explored. It is shown that both capture of quasi-free and localized pre-solvated electrons can adequately explain the observations. The large yield of radical anions at low concentration of polyfluorene enables observation of subsequent chemistry on the picosecond timescale in these systems, that would otherwise been limited by diffusional attachment to the nanosecond regime.