A protocol for the synthesis of 2,4,6-trisubstituted pyridines from the β-nitrostyrenes, available substituted salicylic aldehydes and ammonium acetate was developed. The present strategy features high chemoselectivity and excellent tolerance for a broad range of functional groups, in which the β-nitrostyrenes generated from aldehydes and nitromethane, substituted salicylic aldehydes and ammonium acetate were respectively employed as simple and easily available substrates. This efficient method provides fast access to a variety of structurally diverse pyridine derivatives. The structures of two typical products were confirmed by X-ray crystallography.