Low-ceiling temperature polymers with triggered transience have gained attention due to their potential applications in multiple fields, ranging from lithography to decomposable packaging, as well as for channel manufacturing in microfluidic devices. Besides the development of novel transient materials, advanced electrospinning techniques have also been utilized to increase a materials surface area, which can result in a faster decomposition rate. Thus, it would be of interest to explore the unique characterization of electrospun transient fiber mats made of low-ceiling temperature polymers and their potential usage as support substrate for microelectronic devices. This work reports the first transient electrospun nanofiber mat triggered by UV-irradiation using poly(propylene carbonate) (PPC)/poly(phthalaldehyde) (cPPA) polymer blends. The ability to trigger room temperature transience in nanofibers mats without the need for additional heat or solvent expands its utility in non-biological fields, especially for transient electronic devices. The addition of a photoacid-generator (PAG) to the system working in combination with UV light provides an acid source to enhance degradation since both polymer backbones are acid-sensitive. Electrospinning enables the production of PPC/cPPA composite nanofiber mats capable significant degradation upon exposure to UV radiation while maintaining relatively high mechanical properties. An acid amplifier (AA), an auto-catalytically decomposing compound triggered by acid, was used to generate more acid and accelerate nanofiber degradation. The electrospun fiber mats can be post-annealed to achieve an improved mat mechanical strength of ~ 170 MPa.