Ciprofloxacin (CIP), a widely used broad-spectrum antibiotic, poses a serious threat to human health and environmental safety due to its residues. The complementary monomers molecularly imprinted electrochemiluminescence sensor (MIECLS) based on a polyvinylpyrrolidone-functionalized copper nanowires (CuNWs@PVP) luminescent probe was constructed for the ultra-sensitive detection of CIP. CuNWs with low cost and high conductivity exhibited near-infrared electrochemiluminescence (NIR ECL) properties, yet their self-aggregation and oxidation led to a weakened emission phenomenon. PVP with solvent affinity and large skeleton was in situ attached to CuNWs surface to avoid CuNWs sedimentation and aggregation, and self-enhanced ECL signals were achieved. The bifunctional monomers molecularly imprinted polymer (MIP) possessed complementary active centers that increased their affinity with CIP, enhancing the accurate and sensitive detection of the target substances. The linear range of CIP using MIECLS was 5.00 × 10