In knee replacements, vitamin E-doped ultra-high molecular weight polyethylene (UHMWPE) shows a better wear behavior than standard UHMWPE. Therefore, different sets of polyethylene (PE) acetabular cups, i.e. standard UHMWPE and cross-linked polyethylene irradiated with 50 kGy and 75 kGy, were compared, at a molecular level, with vitamin E-doped UHMWPE to evaluate their wear performance after being tested on a hip joint simulator for five million cycles. Unworn control and worn acetabular cups were analyzed by micro-Raman spectroscopy to gain insight into the effects of wear on the microstructure and phase composition of PE. Macroscopic wear was evaluated through mass loss measurements. The data showed that the samples could be divided into two groups: 1) standard and vitamin E-doped cups (mass loss of about 100 mg) and 2) the cross-linked cups (mass loss of about 30-40 mg). Micro-Raman spectroscopy disclosed different wear mechanisms in the four sets of acetabular cups, which were related to surface topography data. The vitamin E-doped samples did not show a better wear behavior than the cross-linked ones in terms of either mass loss or morphology changes. However, they showed lower variation at the morphological level (lower changes in phase composition) than the UHMWPE cups, thus confirming a certain protecting role of vitamin E against microstructural changes induced by wear testing.