Polypropylene and PA66 are widely used in our daily life, but they cannot be welded by laser transmission welding (LTW) because of polar differences and poor compatibility. In this paper, grafting modification technology is used to improve the welding performance between polypropylene and PA66. Firstly, the strong reactive and polar maleic-anhydride (MAH) is grafted to polypropylene and infrared spectrometer is used to prove that MAH has been grafted to polypropylene. At the same time, the mechanical and thermal properties of the graft modified polypropylene (TGMPP) are tested. The results prove that the grafting modification has little influence on them. Also, the optical properties of TGMPP are measured. Then, the high welding strength between TGMPP and PA66 is found and the mechanism of the weldability is researched, which shows that there are two reasons for the high welding strength. By observing the micro morphology of the welding zone, one reason found is that the modification of polypropylene can improve the compatibility between polypropylene and PA66 and make them easy to diffuse mutually, which causes many locking structures formed in the welding region. The other reason is that there are chemical reactions between TGMPP and PA66 proved by the X-ray photoelectron spectrometer.