In postmastectomy radiation therapy (PMRT), the adequate skin surface dose remains a problem. In this study, the effect of different CTV shrinkage and Skin flash margins on skin dose was investigated, and the accuracy of skin surface dose calculated by TPS for PMRT using thermoluminescent dosimeters (TLDs) was evaluated. Eighty-eight measurement points were determined on the Alderson Rando phantom. To determine the effects of shrinkage margin on skin dose, separate CTVs were generated for 2 mm, 3 mm and 5 mm shrinkage. The prescribed dose was 50 Gy to CTV with a daily fraction dose of 2 Gy. A total of 12 plans were created using four different skin flash thicknesses for each CTV shrinkage margin. After applying 0 mm, 10 mm, 15 mm and 20 mm skin flash thicknesses for each area of the 7F-IMRT treatment plan, the plans were recalculated, and the SF-0, SF-10, SF-15 and SF-20 plans were created, respectively. The increase in skin flash thickness in IMRT plans resulted in a significant increase in skin dose. There was a significant difference between TPS and TLD doses in all chest wall areas for SF-0, SF-10, and SF-15 (p < 0.05). However, there was no significant difference in all areas of the chest wall for SF-20 (p > 0.05). The shrinkage margin thickness of the CTV was found to be inversely proportional to the skin dose for all treatment plans. In tumors near the surface, bolus or skin flash techniques can get the skin adequately dosed. However, the skin flash technique has shown superiority in the application. In PMRT, it is recommended to keep the shrinkage margin as small as possible and use the skin flash thickness of 20 mm for the skin to receive a sufficient dose.