Photothermal electrospinning (PTE) represents an innovative fusion of electrospinning (ES) technology and photothermal therapy (PTT), where photothermal agents (PTAs) are incorporated into electrospun fibers to enable localized thermal effects under near-infrared (NIR) irradiation. The high surface area and tunable architecture of electrospun fibers provide an ideal platform for efficient PTA loading, while the precise temperature control and therapeutic efficacy of PTT significantly broaden its biomedical applications, including antibacterial therapy, anticancer treatment, tissue regeneration, and drug delivery. This review mainly focuses on the emerging field of PTE. Following an overview of the basic PTE parts (ES, PTAs, and PTT), the fabrication strategies (one- and two-step methods) of photothermal electrospun fibers and their latest advancements in both antibacterial and non-antibacterial applications are summarized. Furthermore, the current challenges are deliberated at the end of this review.