Response of port wine stain (PWS) to photodynamic therapy treatment (PDT) is variable and depends on treatment setting used and anatomic sites as well as on size and depth of ectatic vessels. Optical coherence tomography (OCT) is a non-destructive imaging modality which can reveal the layered structure of the upper part of the skin. The structural features of the PWS skin such as the diameter and depth of the blood vessels in different anatomic sites can be showed in the OCT images. In this study, the possible role of PWS skin structure in the response to PDT is assessed. 82 positions from 43 patients with PWS underwent OCT evaluation in cheek, zygomatic aera, preauricular and temporal region before and 3~4 months after the first PDT when treatment outcomes were also evaluated. After analyzing the structural features in different anatomic sites and the therapeutic effect of them, we found that the ectatic vessels diameter was obvious bigger in the cheek which had slightly poorer outcomes than other areas. Some typical structures had poor or good outcomes after first PDT. These can help the clinic doctors predict the response of some patients which have typical structures after PDT treatment. The OCT will be a potential tool for prediction of treatment response for port wine stain after photodynamic therapy.