Nanofabrication using electrochemical deposition ("plating") is an attractive option due to its running and equipment cost effectiveness. It allows an easy control of the deposition process with high degree of reproducibility through the possibility of adjusting a range of parameters such as voltage/current program, time, temperature, plating bath composition etc. Diverse template methods are currently popular to fabricate periodic arays of metal nanoscopic objects or patterns. However, nanostructured deposits can be achieved also by template-free electrodeposition. Volmer-Weber growth, leading directly to nanostructured metal deposits can be achieved at high overpotentials for the systems with low exchange current densities. Such deposition conditions are met at low concentrations of metal cations to be electroreduced onto a support material for which the heterogenous electron transfer rate is low. Electrochemical dissolution of metal anodes in unsupported medium such as water generates metal oxide/hydroxide material, which can be deposited on a substrate connected as a cathode in the electrochmical cell. Depending on the properties of anode-derived material (zeta potential and conductivity), metal electroreduction or electrophoretic deposition of anode-derived material can be achieved. The above-described strategy is used to deposit silver onto silicon and copper, nickel and copper-copper nickel alloy onto carbon fiber microelectrodes. The nanostructured deposits can be applied as amperometric and SERS sensors.