The use of 2-deoxy-2-[¹⁸F]fluoro-D-glucose ([¹⁸F]FDG) positron emission tomography (PET) has been a cornerstone in the metabolic imaging of breast cancer. However, its limitations in specific subtypes and clinical scenarios have driven the exploration of new frontiers in clinical PET imaging. This review highlights the role of emerging alternatives, such as PET [¹⁸F]16α-Fluoroestradiol ([¹⁸F]FES), Human Epidermal Growth Factor Receptor 2 (HER2)-targeted imaging, and Fibroblast Activation Protein (FAP) imaging. PET [¹⁸F]FES can play a pivotal role in the assessment of estrogen receptor (ER) expression. Similarly, HER2-targeted PET imaging facilitates non-invasive, whole-body assessment of HER2 expression. These tracers allow the detection of intra-patient, inter-lesional heterogeneity, synchronous and metachronous, offering valuable insights into equivocal lesions and also hold a predictive value, guiding treatment decisions and optimizing therapeutic strategies. PET FAP, which targets cancer-associated fibroblasts, provides unique information on tumor microenvironment, with potential clinical application for an improved staging and restaging in tumors with low [¹⁸F]FDG uptake, such as lobular breast cancer. Complementary to [¹⁸F]FDG PET, these tracers enable a more personalized approach to breast cancer management with a significant potential to advance precision oncology.