The coordination of pyridyl-N to pentacyanoferrate for the detection of small organic antigens in solution is presented. The unique contribution of this paper is the direct conjugation of pyridyl-N in small organic antigens to pentacyanoferrate. Pentacyanoferrate is promising as an electrochemical label owing to its good electro-chemical properties, which can be utilized to generate an electrical signal in homogeneous electrochemical immunoassays. The facilely synthesized pyridyl-N to pentacyanoferrate was characterized by the electrochemical and spectroscopic methods. Hippuric acid (HA) has been detected competitively on the interaction of free HA and pentacyanoferrate-(4-aminomethylpyridine-hippuric acid) (Fe-HA) to its antibody, with the detection limit of 0.50 ${mu}g;mL^{-1}$. While pentacyanoferrate-based immunoassay is in its simplicity and infancy, the proposed immunoassay offers attractive opportunities for developing pyridyl-N-based the electrochemical detection of small organic antigens in the health care area.