This study utilized solvent co-extrusion technology and NaBH4 reduction to fabricate polyketone (PK) hollow fiber membranes with high water permeance and fouling resistance. Variations in reduction reaction time were explored to assess their impact on chemical composition, morphology, and properties. The results showed that the reduction reaction leads to the conversion of carbonyl groups on the membrane surface to hydroxyl groups, and with prolonged reaction time, the amount of hydroxyl groups on the membrane surface increases to a certain extent. The change in membrane chemical composition enhanced the hydrophilicity, while leaving the membrane morphology, mechanical properties, and separation performance largely unaffected. Static adsorption tests with bovine serum albumin (BSA) and E. coli exhibited distinct fouling behavior. While pristine PK membranes displayed significant BSA adsorption, PK reduction significantly reduced it. Both pristine and reduced PK membranes showed minimal E. coli attachment, likely due to weak interactions. Dynamic filtration tests demonstrated excellent flux recovery for reduced PK membranes, especially after 10 min of reduction, indicating superior fouling resistance with high flux recovery and low irreversible fouling, regardless of foulant type. These findings highlight a straightforward and efficient approach for producing high-performance membranes with exceptional fouling resistance suitable for practical applications.