3D magnetic hollow porous CdFe2O4 microspheres (3D MHPS-CdFe2O4) were prepared by a one-step and template-free hydrothermal method. The material was applied for magnetic solid phase extraction of three azo colorants (Acid Red, Congo Red, Sunset Yellow). Compared to conventional CdFe2O4 nanoparticles, the new 3D material exhibits superior extraction capability because of its unique hollow porous structure, high specific surface area, and the strong interaction between 3D microspheres and the colorants. A magnetic solid phase extraction (MPSE) combined with HPLC was established for simultaneous detection of the three azo colorants in food samples. Under optimum conditions, the detection limits are 0.54–1.00 ng mL-1, and good recoveries of 87.0–100.7% were obtained with spiked samples, with relative standard deviation of ≤ 3.8%. The combination of using the new 3D material and MPSE-HPLC results in an efficient, sensitive and inexpensive method for simultaneous determination of such colorants.