Few-layer black phosphorus (BP) is a promising anode material for sodium ion batteries (SIBs) due to its high theoretical capacity and favorable layered structure. However, practical implementation is hindered by sluggish reaction kinetics and large volume change during de/sodiation process. Especially, combining BP with large portion of low-capacity carbonaceous materials is a common strategy to improve the Na storage properties, but leading to reduced specific capacity based on the overall mass of the whole electrode. To address these challenges, nanoscale surface engineering of few-layer BP is herein performed by homogeneously depositing horizontally aligned Poly(3, 4-ethylenedioxythiophene) (PEDOT) nanofibers on specially surface-modified BP nanosheets. Such material design could achieve simultaneously: (1) enhanced charge transfer kinetics and (2) super surface wettability with electrolyte. Benefiting from the unique functionalization, the reaction kinetics are greatly enhanced accordingly for both sodium and lithium storage. Our strategy sheds light on designing advanced electrodes for high-performance rechargeable batteries and other energy storage/conversion devices.