The convergence of nanotechnology and tissue engineering has paved the way for innovative cancer treatments that leverage the unique light absorption properties of nanomaterials. Indeed, photothermal therapy (PTT) and photodynamic therapy (PDT) utilize nanomaterials to convert near-infrared light into therapeutic energy for cancer treatment. This study focuses on the application of poly(lactic-co-glycolic acid) (PLGA) scaffolds, enhanced by graphene oxide, Ti3C2Tx MXene, and TiS2 transition metal dichalcogenides for PDT and PTT treatments evaluated within 3D-bioprinted breast cancers. Our scaffolds were designed to exploit the photothermal conversion efficiency and capability to generate reactive oxygen species (ROS) to compare the specific features of each 2D material. We demonstrated a reduction in tumor viability under scaffold irradiation, along with the exploration of biological responses to damage such as autophagy and pyroptosis, verifying that these scaffolds can differentially induce these processes depending on the light responsiveness of each material. The integration of these materials within 3D-printed scaffolds does not only enhance the therapeutic efficacy of PTT and PDT, but also offers a precise method to control the cellular environment after therapy, i.e. tissue regeneration and antibacterial effects, providing insights into the potential for these technologies to be adapted for personalized medicine for breast cancer treatment and reconstruction.