Sizing electrodes is an important step during Lithium-ion battery manufacturing processes since poor cut edge affects battery performance significantly and sometime leads to fire hazard. Mechanical cutting could result in a poor cut quality with defects. The cutting quality can be improved by using a laser, due to its high energy concentration, fast processing time, small heat-affected zone, and high precision. The cutting quality is highly influenced by operating parameters such as laser power and scanning speed. Thus, we studied a numerical simulation to provide a guideline for achieving clear edge quality. In order to simulate electrodes laser cutting for Lithium-Ion batteries, understanding the behavior of current collectors is crucial. This study focuses on current collectors, such as pure copper and aluminium. Numerical studies utilized a 3D self-consistent mathematical model for laser–material interaction. Observations of penetration time, depth, and threshold during laser cutting processes of current collectors are described. The model is validated experimentally by cutting current collectors and single side-coated electrodes with a single mode fiber laser. The copper laser cutting is laser intensity and interaction time dependent process. The aluminium laser cutting depends more on laser intensity than the interaction time. Numerical and experimental results show good agreement.