Background. A group of cardiopathies (ischemic, arrhythmic, and pericardial cardiac events) were shown to be associated with doses received by heart substructures following radiotherapy, alerting about the importance of dosimetric evaluation of cardiac structures besides the heart. The aim of this study was to assess the dosimetry of heart and heart substructures of left-sided breast cancer radiotherapy to evaluate possible radiation-induced complications. Methods and Materials. The study enrolled 20 patients treated with 3D-conformal radiotherapy (3DCRT), while intensity-modulated (IMRT) and volumetric-modulated arc radiotherapy (VMAT) plans were simulated for comparative purposes. The organs at risk (OARs) of interest were the heart, ascending aorta, descending aorta, left ventricle, left atrium, right ventricle, right atrium, superior vena cava, inferior vena cava, and pulmonary artery. Results. The percentage of left ventricle included in the radiation field was >5% for all plans (8.92% 3DCRT, 8.30% IMRT, and 6.84% VMAT). A strong correlation between mean heart dose and the percentage of left ventricle overlapping with the radiation fields was observed in 3DCRT (r = 0.784) and IMRT (r = 0.755) plans, and a moderate correlation was shown between tumor volume and the percentage of left ventricle included in the radiation field for all plans. A moderate correlation was observed between body mass index and cardiac structures for the mean dose to the right ventricle (r = 0.640) in conformal plans and V5 of heart (r = 0.528) and left ventricle (r = 0.669) in volumetric-modulated plans. Additionally, moderate to strong correlations were found between maximum heart distance and heart dose in both conformal and modulated plans. Conclusions. Considering possible occurrences of cardiac events during or postradiotherapy, monitoring the heart and its substructures and setting dosimetric thresholds for healthy tissues must be a priority to achieve a personalized and effective treatment.