The effects of three organic colorants on photo-initiated crosslinking and photo-oxidation degradation of polyethylene (PE) samples irradiated by microwave excited (MWE) UV lamp in the melt and the related mechanism have been studied by gel content and thermal extension rate determinations, X-ray photoelectron spectroscopy (XPS), mechanical property tests, UV spectroscopy, and light microscope. The data from the gel content and thermal extension rate determinations of photo-crosslinked polyethylene (XLPE) samples show that the three colorants can decrease the efficiency of photo-initiated crosslinking of polyethylene to some different degree, in which the effect of red colorant is the largest among the three colorants. The colorized samples of 1 mm thickness are easily to be crosslinked to a satisfactory gel content of about 70% by the MWE lamp and optimized reaction conditions, such as the concentration of colorant, irradiation time,and so on. The XPS results give the evidence that the colorants can accelerate the surface photo-oxidation during the photo-crosslinking of polyethylene. The photo-oxidation products such as -CH2-O-and-C(C=O)-groups on the surface of XLPE samples with the colorants apparently increase with increasing the irradiation time. The data from the mechanical tests show that the colorants reduce the tensile strength and improve the elongation at break of XLPE samples. All the above results show that the effects of the three colorants on photo-initiated crosslinking and photo-oxidative degradation decrease with the order of red ＞ blue ＞ green colorants. The light microscope photos show that the colorant can disperse well in PE resin. The mechanism of the colorant effects can be elucidated by comparison of the UV absorption spectra of photo-initiator and colorants. This is because the colorants absorb the same UV wavelength regions as photo-initiator, and thus decrease the photo-crosslinking efficiency of photo-initiator and accelerate the surface photo-oxidation of XLPE materials.