Although several studies have reported that the addition of bamboo charcoal (BC) to polylactide (PLA) enhances the properties of PLA, to date, no study has been reported on the fabrication of ultrafine BC/poly(L-lactide) (PLLA) webs via electrospinning. Therefore, ultrafine fiber webs of PLLA and BC/PLLA were prepared using PLLA and BC/PLLA raw fibers via a novel laser electrospinning method. Ultrafine PLLA and BC/PLLA fibers with average diameters of approximately 1 μm and coefficients of variation of 13–23 and 20–46% were obtained. Via wide-angle X-ray diffraction (WAXD) analysis, highly oriented crystals were detected in the raw fibers; however, WAXD patterns of both PLLA and BC/PLLA webs implied an amorphous structure of PLLA. Polarizing microscopy images revealed that the webs comprised ultrafine fibers with uniform diameters and wide variations in birefringence. Temperature-modulated differential scanning calorimetry measurements indicated that the degree of order of the crystals in the fibers was lower and the molecules in the fibers had higher mobilities than those in the raw fibers. Transmittance of BC/PLLA webs with an area density of 2.6 mg/cm2 suggested that the addition of BC improved UV-shielding efficiencies.