Nanometer molecularly imprinted polymers (nano‐MIPs) spherical particles with specific recognition of sialic acid (SA) are synthesized by electrochemically mediated atomic transfer radical polymerization combined with the precipitation method. SA is used as template molecules,4‐vinylphenylboronicacid as functional monomer, and ethylene glycol dimethacrylate as the crosslinking agent. The successful synthesis of spherical nano‐MIPs is verified by Fourier transform infrared spectroscopy, scanning electron microscope, and Malvern particle size instruments. The effects of the potential adjustment on the morphology, size, and particle size distribution of MIP particles are further investigated. By adjusting the potential for polymerization, nanoparticles with average sizes of 160.32, 275.87, and 331.99 nm are obtained. The recognition performance of nano‐MIPs for SA is characterized by a UV–vis spectrophotometer and the satisfactory imprinting factor is 1.54.