The recovery of lithium ions from mixed solutions has attracted extensive research interests with increasing demand of lithium resources. In this study, novel cauliflower-like lithium-ion imprinted polymers (Li-IIPs) have been successfully synthesized by using B12C4 as the complexing agent, acrylamide (AM) as the functional monomer and N,N′-methylene bis-acrylamide (MBAM) as the cross linker for selective separation and recovery of lithium ions from mixed solutions. The Li-IIPs exhibited maximum adsorption capacity for Li⁺ (1.135 mmol g⁻¹) under optimum experimental conditions. Additionally, the high relative selectivity factors (K_Li/Na = 5.34, K_Li/K = 6.47, K_Li/Cu = 23.05, K_Li/Zn = 27.13) indicated that Li-IIPs had outstanding selective performance. The regeneration experiments were also conducted and confirmed the favorable reusability and stability of the as-prepared polymers. Therefore, the outstanding performance and simple preparation method makes Li-IIPs a powerful tool for effective separation and recovery of lithium ions in practical applications.