Customized fabrication of electrodes for electro-discharge machining (EDM) is considered as a useful emerging application of metal additive manufacturing technologies for building complex shaped tools in a short period of time. This approach of producing electrodes not only effectively addresses the design flexibility and complexity issues of the tools but also enables the use of various materials so as to ingrain the desired properties in them. The current study explores the production of laser powder bed fusion (LPBF) AlSi10Mg tools for machining of titanium alloy. Moreover, it explicitly assesses the machining performance of additively manufactured electrodes when the tools are subjected to a thin layer of copper coating. Three types of acidic baths are used for electroless coating of tools. The machining performance of the tools in terms of material removal rate, tool wear rate, surface crack density, surface roughness, white layer thickness, and microhardness of the white layer is compared for different electroless copper coating processes. It is observed that the coated tools significantly enhance material removal rate; however, uncoated LPBF tools exhibit superior surface morphology and surface roughness.