In this work, laser-heated electrospinning (LES) process using carbon dioxide laser was explored as an eco-friendly method for producing ultrafine fibers. To enhance the thinning of fibers and the formation of fiber structure, planar or equibiaxial stretching and subsequent annealing processes were applied to poly(ethylene terephthalate) (PET) fiber webs prepared by LES. The structure and properties of the obtained webs were investigated. Ultrafine fiber webs with an average diameter of approximately 1 μm and a coefficient of variation of 20-25% were obtained when the stretch ratios in the MD (machine direction) × TD (transverse direction) were 3 × 1 and 3 × 3 for the planar and equibiaxial stretching, respectively. In the wide-angle X-ray diffraction analysis of the web samples, preferential orientation of crystalline c-axis were confirmed along the MD for planar stretching and only along the web plane for equibiaxial stretching, which was in contrast to the stretching of film samples, where additional preferential orientation of benzene ring along the film plane proceeded. The results obtained suggest that PET fiber webs fabricated through LES and subsequent planar or biaxial stretching processes have potential for a wide variety of applications, such as packaging and battery separator materials.