The controllable assembly of metal-organic frameworks (MOFs) nanomaterials is an effective means to enhance their application capabilities. In this paper, a novel method is reported to control MOFs assembly by using a DNA framework material, a tetrahedral DNA nanostructure (TDN) labeled with phosphate groups at the vertex. In particular, various well-defined superstructures can be tailored by regulating the number of phosphate groups that coordinate with catalytic Zr-MOFs to create polymeric MOFs superstructures (Poly(MOFs)), exhibiting excellent catalytic activities and molecular recognition ability as well as greatly amplified signal readout. Furthermore, based on the DNA framework-controlled Poly(MOFs), a colorimetric biosensor with excellent analytical performance is fabricated for improving the diagnosis of human epidermal growth factor receptor 2 (HER2)-positive breast cancer. It is demonstrated that the quantification of HER2 protein can be achieved at molecular level with the limit of detection (LOD) of 12 pg L-1 and cellular level with the LOD of 10 cells. More importantly, the detection of HER2 in the serum of breast cancer patients have been achieved, thus HER2-positive and triple-negative breast cancer patients can be well distinguished. Considering the substitutability of the target, this study shows great potential in biomedical research as well as clinical applications.