We demonstrate that novel three-dimensional (3D) B(OH)3 and α-Fe2O3 nanoparticles decorated carbon microspheres (B(OH)3/α-Fe2O3-CMSs) can be fabricated via a facile thermal treatment process. The carbon microspheres with diameter of 1 to 3 μm and decorated B(OH)3 and α-Fe2O3 nanoparticles with diameters of several to tens of nanometers are successfully fabricated. These novel 3D B(OH)3/α-Fe2O3-CMS composites exhibit enhanced microwave absorption with tunable strong absorption wavebands in the frequency range of 2–18 GHz. They have a minimum reflection loss (RL) value of -52.69 dB at a thickness of 3.0 mm, and the effective absorption bandwidth for RL less than -10 dB is as large as 5.64 GHz. The enhanced microwave absorption performance arises from the synergy of the impedance matching caused by the B(OH)3 nanoparticles, dielectric loss as well as the enhancement of multiple reflection among 3D α-Fe2O3 nanocrystals. These results provide a new strategy to tune electromagnetic properties and enhance the capacity of high-efficient microwave absorbers.