Multifunctional Prussian blue analogs (PBAs) have received extensive attention in the detection and degradation of food hazards. However, the development of new structural adjustment strategies to further improve their performance remains a huge challenge. Herein, the "interface recombination" post-processing approach was established to regulate the structure of PBAs using a microwave-assisted solvothermal method combined with acid etching. Hollow cube-shaped M-NiMnFe-PBA with elevated peroxidase-mimetic activity, photothermal effect, and photo-Fenton performance was obtained. Based on M-NiMnFe-PBA, a dual-mode nanoenzyme-linked immunoassay sensing platform was constructed for aflatoxins B1 (AFB1) detection, achieving low detection limits of 4.96 fg/mL in the colorimetric mode and 1.5 pg/mL in the photothermal mode. Due to its admirable photo-Fenton performance, AFB1 was almost completely degraded within 3 h, resulting in a significant reduction in its cytotoxicity. This work provides a new solution for synthetic regulation and property enhancement of PBAs, which promotes their application in control of food hazards.