Cationic organic polymers have found relatively extensive utility for TcO4-/ReO4- removal, but the harsh preparation conditions constrain their practical application. The bifunctional guanidinium-based cationic organic polymer (GBCOP) was successfully and facilely synthesized in benign conditions within 1 h. Batch experiments showed that GBCOP exhibited rapid removal kinetics (1 min, >98.0%) and a substantial removal capacity of 536.8 mg/g for ReO4-. Even in 1000-fold co-existing NO3- anions, the removal efficiency of GBCOP for ReO4- was 74.0%, indicating its good selectivity. Moreover, GBCOP had high removal efficiencies for ReO4- across a wide pH (3.0–10.0) range and presented remarkable stability under the conditions of strong acid and base. GBCOP could be reused four times while removing 80.8% ReO4- from simulated Hanford wastewater. SEM and XPS results revealed that the mechanism of ReO4- removal involved Cl- ion exchange within the channels of GBCOP. Theoretical calculation results supported that existing the strong electrostatic interaction between guanidinium and ReO4-. This dual-function GBCOP material is cost-effective and holds significant potential for large-scale preparation, making it a promising solution for TcO4- removal from nuclear wastewater.