In treatments such as post-mastectomy radiation therapy (PMRT) for breast cancer patients, skin doses are of great importance in terms of tumor control and side effects. This dosimetric study aimed to measure the skin dose on the chest wall surface for post-mastectomy radiotherapy with Tomotherapy and Halcyon devices using thermoluminescence dosimetry (TLD) and to evaluate the accuracy of the skin dose calculated by treatment planning systems (TPS). Computed tomography (CT) images of the Alderson Rando phantom were obtained. Treatment plans were created with Tomotherapy and Halycon devices for a total of 50 Gy with a fraction dose of 2 Gy to the target volume. The left chest wall was divided into 9 regions for detailed surface dose assessment. 88 dose measurement points were determined on the left chest wall. The phantom was irradiated separately in Halycon and Tomotherapy devices. In vivo, dose measurements were performed with TLD in both devices. TPS and TLD doses were compared for the left chest wall surface. For skin dose, TLD measurements were lower than the dose estimate by Tomotherapy TPS and higher than the dose estimate by Halycon TPS. In addition, the skin dose measurements showed that the skin dose of the Tomotherapy device was higher than that of the Halycon. It is recommended to consider the distance of the treatment device and the accuracy of the TPS dose calculation in skin dose assessment in PMRT.