With the rapid development of the modern industries, more and more waste cross-linked polyethylene (XLPE) cables are discarded, resulting a serious environmental problem. How to recycle the waste XLPE cables becomes a big challenge worldwide because they cannot be thermally re-processed due to the cross-linking structures. This paper reported a new technology to efficiently recycle waste XLPE cables. XLPE cables were milled by our invented solid-state shear milling (S3M) technology, suffering from the very strong shear forces, the waste XLPE cables were pulverized, a part of the cross-linking bonds were broken, and then could be thermally re-processed. The structure and properties of the milled XLPE were systematically investigated by gel fraction measurement, Fourier transform infrared spectroscopy (FTIR), differential scanning calorimeter (DSC), torque rheological measurement, scanning electron microscope (SEM) and thermo-gravimetric analyzer (TG). The experimental results showed that S3M realized the superfine pulverization of the waste XLPE, obviously destroyed the cross-linking bonds of XLPE and greatly improved its processability. The S3M treated XLPE was used to successfully manufacture geo-membranes with good mechanical properties in an industrial scale. S3M technology is an effective method to recycle the waste XLPE.This work is supported by National High Technology Research and Development Program of China (863 program) (2012AA063003) and National Natural Science Foundation of China (51121001).