The in situ generation of 3-diazonium cations from 3-aminopyridine and their subsequent stability under experimental conditions used for electrografting of pyridine groups were investigated by spectroscopy and electrochemistry. UV spectroscopy revealed the rapid kinetics for the reaction of 3-aminopyridine with sodium nitrite in HCl to form the 3-diazopyridinium cation with a second-order rate constant of 550 +/- 20 L mol(-1) s(-1) at 22 degrees C. UV spectroscopy showed that the 3-diazopyridinium ion was relatively unstable and its transformation into 3-hydroxypyridine was proven by H-1 NMR. Its hydrolytic decomposition was investigated by NMR and followed first-order kinetics with a rate constant of (53 +/- 5) X 10(-3) s(-1) at 22 degrees C. These result; enable us to establish the appropriate conditions for the electrografting of pyridine from the corresponding diazoniurn cations generated in situ. The electrochemical modification of glassy carbon electrodes with pyridine was characterized by cyclic voltammetry and the resulting grafted layer by electrochemical impedance spectroscopy in the presence of Fe(CN)(6)(3-/4-) as reliox probes. The effect of diazotization time before electrochemical reduction on the blocking effect of the grafted layer was investigated and showed that an increase of the diazotization time led to less efficient grafting. The presence of immobilized pyridine on the electrode surface was demonstrated by X-ray photoelectron spectroscopy measurements, and a surface coverage of 3.8 x 10(-10) mol cm(-2) was estimated for the grafted pyridine groups. The significance of these results for researchers using the in situ generation approach for electrochemical and chemical grafting is discussed.