Newly modified biofibers made up of kenaf fibers (KF) and conducting polyaniline (PANI) were successfully prepared via in situ polymerization. Several characterization methods were done to elucidate the interaction between the KF surfaces and the in situ polymerized PANI. The PANI coated KF (KF/PANI) achieved new electronic properties, without sacrificing its mechanical properties and natural fiber characteristic. Initial mercerization on the KF yielded better PANI coated fibers compared to the untreated KF. Fiber bundle tensile test on the untreated KF/PANI revealed a drop in the unit break of about 48% compared to the untreated neat KF. Meanwhile, the mercerized KF/PANI showed reduction of about 17% compared to the uncoated mercerized KF. The mercerized KF/PANI exhibits polaronic transitions, existence of favorable IR peaks and Raman scattering, enhanced DC conductivity, and better morphological characteristic as a result of the in situ PANI coating. Such electronically modified natural fibers could be suitable as green conducting fillers in composites to replace other synthetic fibers.