The invention relates to a method for carrying out 10kV charged wire connecting operation by a CO2 laser cable peeling device. The CO2 laser cable peeling device is suspended on a live wire; H-shaped notches are cut out at two sides of the live wire respectively; the H-shaped notches at two sides are accurately butted and then form two annular notches at two sides and two coherent longitudinal notches between the two annular notches on the live wire; a cut insulating sheath is peeled off from the live wire; one end of a drainage wire is locked by a lock bar; the drainage wire is sent to a live wire connection position; a round mouth screw type drainage wire clamp is suspended on the live wire with a drainage wire clamp operating rod; a bolt is tightened; and the drainage wire clamp and the wire are tightly fixed. Online peeling is carried out on the live wire by the CO2 laser cable peeling device; a metal cable core is not damaged; the peeling efficiency is high; the notches are accurate; and the reliability of 10kV charged wire connection is greatly improved.