Magnetically recovered Co and Co@Pt catalysts for H2 generation during NaBH4 hydrolysis were successfully synthesized by optimizing the conditions of galvanic replacement method. Commercial aluminum particles with an average size of 80 µm were used as a template for the synthesis of hollow shells of metallic cobalt. Prepared Co0 was also subjected to galvanic replacement reaction to deposit a Pt layer. X-ray diffraction analysis, X-ray photoelectron spectroscopy, scanning electron microscopy, and elemental analysis were used to investigate catalysts at each stage of their synthesis and after catalytic tests. It was established that Co0 hollow microshells show a high hydrogen-generation rate of 1560 mL·min−1·gcat−1 at 40 °C, comparable to that of many magnetic cobalt nanocatalysts. The modification of their surface by platinum (up to 19 at% Pt) linearly increases the catalytic activity up to 5.2 times. The catalysts prepared by the galvanic replacement method are highly stable during cycling. Thus, after recycling and washing off the resulting borate layer, the Co@Pt catalyst with a minimum Pt loading (0.2 at%) exhibits an increase in activity of 34% compared to the initial value. The study shows the activation of the catalyst in the reaction medium with the formation of cobalt–boron-containing active phases.