The formation of a tribological layer (i.e., tribolayer) affects friction and wear behavior during sliding. The mechanisms involved can be better understood by the characterization of this layer. The wear corrosion behavior of Ti-6Al-4V was studied using a reciprocating ball-on-flat tribometer at a frequency of 1 Hz and under normal loads of 1 N, 5 N, and 15 N against an alumina ball for 3600 cycles of sliding in a phosphate buffer saline (PBS) solution. Scanning Electron Microscopy (SEM) images, along with EDS analysis showed a greater coverage of a tribolayer under a normal load of 15 N. Transmission electron microscopy (TEM) studies indicated that a tribolayer with thickness up to 1000 nm, consisting of nanograins with diameters of less than 10 nm, formed on the deformed wear surface of Ti-6Al-4V under a normal load of 15 N. This protected tribolayer, under normal loads of 5 N and 15 N, resulted in a decrease of 40% in the coefficient of friction and a 15–20% reduction in the specific tribocorrosion rate compared with that at the lower applied load.