Vascular endothelial growth factor (VEGF)-vascular endothelial growth factor receptor (VEGFR)pathways are essential in tumor angiogenesis, growth and metastasis. Studies on anti-angiogenic therapy have been mostly focused on the blockage of VEGF-VEGFR pathways. We report an extracellularly transformable peptide-based nanomaterial to develop artificial extracellular matrix(ECM)-like networks for high-efficient blockage of natural VEGF-VEGFR interactions. The transformable peptide-based nanomaterial transforms from nanoparticles into nanofibers upon binding to VEGFR in solution. In addition, the transformable peptide-based nanomaterial forms ECM-like fibrous networks on VEGFR overexpressed cells, inhibiting the VEGF-VEGFR interactions and the subsequent angiogenesis.The tube formation is reduced by nearly 85.1％ after treatment. This strategy shows excellent potential for anti-angiogenesis, and inhibition of tumor invasion and metastasis.