Superparamagnetic nanoparticles of modified vitamin B3 (Fe3O4@Niacin) represent a new, efficient and green biocatalyst for the one‐pot synthesis of 2‐amino‐3‐cyanopyridine derivatives via four‐component condensation reaction between aldehydes, ketones, malononitrile, and ammonium acetate under microwave irradiation in water. This new magnetic organocatalyst was easily isolated from the reaction mixture by magnetic decantation using an external magnet and reused at least six times without significant degradation in the activity. The catalyst was fully characterized by FT‐IR, XRD, SEM, VSM, UV–Vis, DLS and EDS. Excellent yield, very short reaction time (7–10 min), operational simplicity, easy work‐up procedure, avoidance of hazardous or toxic catalysts and organic solvents are the main advantages of this green methodology which makes it more economic than the other conventional methods.