While Prussia Blue analogues (PBs) are promising catalysts, PBs are typically prepared to be nanoscale, making them less practical especially for solution-based reactions. Although a few attempts have developed substrate supported PBs, many of them are still very small and PB is not grown homogeneously. However, there is still an urgent demand for developing substrate-supported PB which is catalytically effective, convenient-to-prepare, simple-to-use and easy-to-recover. To this end, a macrosphere-supported nanoscale PB is proposed using ion exchange resins as readily available, robust and functionalized macrospheres. Through layer-by-layer impregnating resins in cobalt and hexacyanoferrate solutions, PB is grown on the surface of resins via self-assembling. Both cation and anion exchange resins (CR and AR) can be successfully employed to grown PB through the same self-assembling technique. The resulting PB@R can preserve porous structures and metal coordination of PB, and easy-to-handle features of resins, making them promising catalysts for aqueous catalytic reactions. As 4-NP reduction is selected as a model reductive reaction, PB@R quickly reduces 4-NP to 4-AP in the presence of NaBH4 and exhibits a much lower Ea compared to other reported precious metal catalysts. PB@R can also activate PMS to generate sulfate radicals to degrade organic pollutants. PB@R can be also packed in a column for continuous flow-through reductive and oxidative reactions. These results indicate that PB@R is a conveniently prepared and highly effective and stable macro-spherical catalyst for aqueous environmental catalysis. The preparation scheme here can be also applied to fabricate other versatile macrosphere-supported metal complex catalysts.