Wearable electronics, regarded as the next generation of conventional textiles, have been an important concept in the study of e-textiles. Conductive fibres are the upstreaming of e-textiles and have witnessed the booming development in recent years. However, little work has focused on improving the wash ability and durability of conductive fibres. As a new approach to manufacturing conductive fibres, Polymer Interface Molecular Engineering (PIME) is starting to be employed recently, to build up an interfacial layer on polymeric fibre surfaces; this interfacial layer services as a platform to anchor catalysts for the following metal Electroless Deposition (ELD). The designed interfacial layer significantly increases adhesion between polymeric substrates and coating metal layers, to improve the durability of e-textiles. This review highlights recent research into different molecular and architectural design strategies, and its potential application for wearable electronics. Further challenges and opportunities in this field are also discussed critically.