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In order to improve the long-term reliability of XLPE cables, it is essential to understand the mechanism of deterioration and breakdown as a result of long-term voltage application. This paper presents the results of our study on the deterioration mechanism of polyethylene, which is the insulating material of XLPE cables, focusing mainly on the electrical deterioration luminescence phenomenon observed using model samples that simulate the regions of high electric field enhancement, e. g., impurities and protrusions. A report is also given on an evaluation of the long-life characteristics of the insulating material, based on electrical deterioration luminescence measurements that take into account the above deterioration mechanism.