Post-mastectomy radiation therapy (PMRT) is an important component in the management of breast cancer patients who have undergone mastectomy. Intensity-modulated radiation therapy (IMRT) and volumetric-modulated arc therapy (VMAT) are two popular methods of delivering PMRT. With IMRT, high radiation doses are directed at the tumor, while exposure to healthy tissue is kept to a minimum. VMAT, on the other hand, is a more advanced version of IMRT that allows for faster radiation dose delivery while maintaining precision. The complexity of the VMAT treatment planning and delivery process, on the other hand, may increase the risk of technical errors, which can reduce treatment effectiveness. Studies have compared VMAT and IMRT in PMRT for breast cancer patients, but most have found no significant differences in treatment outcomes between the two methods. Individual patient factors such as treatment goals, available resources, and other characteristics may influence the choice between the two techniques. This prospective observational study aimed to compare the dosimetry of two cutting-edge modern radiotherapy techniques for post-mastectomy breast cancer patients receiving hypofractionated doses. For 58 patients with breast cancer, 116 plans for radiotherapy treatment were generated by both VMAT and IMRT. To maintain the uniformity of contouring, every CT image was contoured by the same physician, and Radiotherapy Oncology Group (RTOG) contouring guidelines were strictly followed during contouring. Both techniques had comparable target volume coverage, but VMAT produced a significantly better conformity index than IMRT for both the left (0.71 vs. 0.65) and right (0.72 vs. 0.66) breasts (p-value < 0.05). VMAT plans had significantly higher low-dose spillage to the ipsilateral lung (V5Gy and V10Gy) but significantly lower high-dose spillage (V20Gy, V30Gy, and V40Gy) than IMRT plans (p-value < 0.05). Dmax and Dmean for the ipsilateral lung were comparable for both techniques. When compared to alternative treatment approaches, IMRT treatment plans were found to be more effective in minimizing radiation exposure to the heart for all patients with right-sided breast cancer, resulting in considerably lower levels of Dmean, V5Gy, V10Gy, V20Gy, and V35Gy. Plans for VMAT treatment were found to be significantly superior to left-side chest wall radiotherapy in terms of lower exposure to the heart for higher doses. IMRT plans, on the other hand, were successful in dramatically lowering the levels of Dmax that reached the spinal cord for both right- and left-sided breast cancers. Apart from similar planning target volume (PTV) coverage to IMRT plans, VMAT produced significantly better conformity. VMAT plans have more low-dose spillage to normal tissues, while IMRT plans spare various organs at risk significantly better at lower doses in both right and left-sided breast cancer. VMAT was found to be better at sparing the heart (in left-sided breast cancer only) and ipsilateral lung at a high dose range. The best radiotherapy approach for breast cancer should be established on an individual basis, taking into account tumor laterality and the risk-benefit ratio.