In the 21st century, chemotherapy stands as a primary treatment method for prevalent diseases, yet drug resistance remains a pressing challenge. Utilizing electrospinning to support chemotherapy drugs offers sustained and controlled release methods in contrast to oral and implantable drug delivery modes, which enable localized treatment of distinct tumor types. Moreover, the core–sheath structure in electrospinning bears advantages in dual-drug loading: the core and sheath layers can carry different drugs, facilitating collaborative treatment to counter chemotherapy drug resistance. This approach minimizes patient discomfort associated with multiple-drug administration. Electrospun fibers not only transport drugs but can also integrate metal particles and targeted compounds, enabling combinations of chemotherapy with magnetic and heat therapies for comprehensive cancer treatment. This review delves into electrospinning preparation techniques and drug delivery methods tailored to various cancers, foreseeing their promising roles in cancer treatment.