The class III lanthipeptide synthetase (LanKC) installs unusual amino acids, such as lanthionine and labionin, in lanthipeptides. Through genome mining, we discovered a new class III lanthipeptide synthetase coding gene (nptKC) and precursor peptide coding genes (nptA1, nptA2, and nptA3) in the genome of the actinobacterium Nocardiopsis alba. Coexpression experiments of the biosynthetic genes in Escherichia coli resulted in the production of new lanthipeptides named nocardiopeptins A1-A3. Analysis of two-dimensional NMR spectra after enzymatic degradation and partial basic hydrolysis of nocardiopeptin A2 revealed that labionin was located in lanthionine with opposite orientations, forming a nesting structure in nocardiopeptin A2. To the best of our knowledge, this bridging pattern in the lanthipeptides was unprecedented, indicating a novel reaction characteristic of the class III lanthipeptide synthetase NptKC.