To achieve an efficient lubricated interface on titanium alloy (Ti6Al4V) alloy, polyelectrolyte multilayer (PEM) polymer coatings, based on poly(ethyleneimine)/poly(acrylic acid) (PEI/PAA), were fabricated on the surface of Ti6Al4V alloy substrates using the layer-by-layer (LbL) assembly technique. Their composition and morphology were confirmed by Fourier-transform infrared/attenuated total reflectance (FTIR/ATR) spectroscopy, X-ray photoelectron spectroscopy, and scanning electron microscopy. The tribological properties were investigated by a ball-on-disk rotating tribometer using deionized water, saline, and calf serum. The results exhibit that (PEI/PAA)*n coatings have the internal cross-linked network and porous structure on the surface. The surface of PEI/PAA coatings-modified Ti6Al4V shows the sufficient wettability. The polymer-bearing interface of (PEI/PAA)*10 exhibits a low friction coefficient, 0.059, for 2 hr, and represents an 88% decline compared with bare Ti6Al4V. Moreover, the wear track on the polymer-bearing interface is superlow. There is no obvious wear volume, which indicates effective wear resistance. The hydrated layer, the cross-linked network structure, and the porous structure of PEM coatings are the main factors for efficient tribological properties. The multilayer PEI/PAA coating shows the potential uses of developing the lubricated-bearing interface on Ti6Al4V alloy.