Hollow metallic composite particles are widely used in microwave absorption and catalysis due to their unique cavity structures, and favorable physical and electromagnetic properties. In this work, we propose an approach to prepare highly dispersed Fe3O4/Ag composite particles with a hollow structure using water-soluble green template method combined with in-situ growth process. The as-prepared cubic Fe3O4/Ag composite particles with an average size of 3.19 μm of hollow Ag and 11.65 nm of Fe3O4 coating on the surface were used as fillers for preparing microwave absorption epoxy resin films, showing a minimum reflection loss of −62.37 dB at 16.63 GHz with 7.5 mm thickness. An effective absorption bandwidth of 4.80 GHz can be observed in the frequency bands of 4.70–6.09 and 14.59–18.00 GHz. This mechanism is attributed to the internal cavity of the Fe3O4/Ag particles realizing multiple reflections of electromagnetic waves, and the synergistic effect of Fe3O4 and Ag. Moreover, this perspective is confirmed by their photocatalytic performance. The Fe3O4/Ag particles achieve a high photocatalytic degradation efficiency of 99.84% for Congo red dye within 30 min of light exposure and maintain a value of 96.62% after 6 cycles, demonstrating an outstanding reusability.