Hollow Pd–Fe bimetallic magnetic spheres are synthesized in this work. Such materials are successfully characterized by ICP-AES, XPS, TEM, BET, XRD, and VSM, etc. These as-prepared hollow materials have high catalytic activity during Suzuki cross-coupling reactions between aryl halides and arylboronic acids in water. Meanwhile, the catalytic activity can be adjusted via changing the composition of the catalyst. The enhanced activity was attributed to both the hollow chamber structure and the promotional effect of Fe-dopants, which provided more Pd active sites during the reaction. Besides, due to the incorporation of ferrum, the recycling processes of the magnetic catalyst became simpler and more efficient.