Pyropheophorbide‐a (Pyro) is a promising multifunctional molecule for multimodal tumour imaging and photodynamic therapy, but its clinical applications are seriously restricted by the limited tumour accumulation capability. Here, we designed and synthesized a small‐molecule probe that achieved specific dual‐modal tumour imaging based on Pyro. Briefly, a novel molecule combining Pyro, an RGD dimer peptide (3PRGD2) and 64Cu, was designed and synthesized, and the obtained molecule, 64Cu‐Pyro‐3PRGD2, exhibited high tumour specificity in both positron emission tomography and optical imaging in vivo. c (RGDfk) peptide blocking significantly reduced the efficacy of the probe, which confirmed the integrin αVβ3 targeting of this molecular probe. 64Cu‐Pyro‐3PRGD2 had very low accumulation in normal organs and could be rapidly cleared through kidney metabolism, which prevented the potential damage to adjacent normal tissues. Overall, combining tumour targeting, dual‐modal imaging, and biosafety, 64Cu‐Pyro‐3PRGD2 has the potential for clinical use as a molecular imaging probe for tumour diagnosis.