Porous nanowires are of great interest for applications in solar cells, thermoelectrics, gas sensors, fuel cells and catalysis. Here we report on a general methodology for NWs with highly ordered connected macroporosity using a low-cost and scalable synthesis method based on the combination of hard templating with electrodeposition. The greatly improved catalytic performance of these porous NWs (ca. 600% increasing compared to dense NWs) in the hydrolysis of ammonia borane makes them exciting materials for the implementation of hydrolytic boron hydrides as hydrogen carriers for fuel cell applications.