It is provided a self-healing polymer network comprising transition metal thiolates, particularly thiolates of a transition metal that is able to self-assemble by metallophilic attractions, and more particularly Au(I), Ag(I), Cu(I) thiolates, or a mixture thereof, and, optionally, disulfide bonds, thiol and other thiolate groups. It is also provided several processes for the preparation of the self-healing polymer networks of the invention, as well as uses thereof.