Prostate-specific membrane antigen (PSMA) is an excellent target for cancer detection and therapy. Hypoxia is prevalent in solid tumors, and various nitroimidazole (NI) radioligands can be trapped inside hypoxic cells for diagnosis and therapy. To enhance tumor uptake and retention, we designed bivalent agents (compounds -) incorporating a hypoxia-sensitive NI-moiety and a PSMA-targeting group. Ligands - were successfully prepared and labeled with Ga or Lu. Among them, [Ga]Ga- ([Ga]Ga-AAZTA-NI-PSMA-093) demonstrated significantly higher cellular accumulation under hypoxic conditions than under normoxic conditions, suggesting hypoxia-selective trapping by the introduction of NI group. PET/CT imaging at 60 min postinjection of [Ga]Ga- revealed high tumor uptake (SUV: 10.68%ID/mL) in the tumor-bearing mice model. SPECT/CT imaging of [Lu]Lu- at 24 and 48 h postinjection demonstrated excellent accumulation and retention. Preliminary studies indicate that [Ga]Ga/[Lu]Lu- may be promising bivalent agents targeting hypoxia and PSMA binding for diagnosis and radiotherapy.