The laser-assisted melt electrospinning (LES) method was utilized for the preparation of poly(L-lactide-co-ε-caprolactone) (PLCL) fibers. During the process, a carbon dioxide laser was irradiated, and voltage was applied to the raw fiber of PLCL. In situ observation of fiber formation behavior revealed that only a single jet was formed from the swelling region under the conditions of low laser power and applied voltage and feeding rate, whereas multiple jets and shots were produced with increases in these parameters. The formation of multiple jets resulted in the preparation of thinner fibers, and under the optimum condition, an average fiber diameter of 0.77 μm and its coefficient of variation of 17% was achieved without the formation of shots. The estimation of tension and stress profiles in the spin-line was also carried out based on the result of in situ observation and the consideration that the forces originated from surface tension, electricity, air friction, and inertia. The higher peak values of tension and stress appearing near the apex of the swelling region corresponded to the formation of thinner fibers for the condition of single-jet ejection. Analyses of the molecular orientation and crystallization of as-spun fibers revealed the formation of a wide variation of higher order structure depending on the spinning conditions.