<jats:title>Abstract</jats:title><jats:p>Two novel aminooligosaccharides were separated from the culture filtrate of <jats:italic>Streptomyces coelicoflavus</jats:italic> ZG0656. Their chemical structures were determined by acidic hydrolysis, electrospray‐ionization tandem mass spectrometry (ESI‐MS/MS), and NMR spectroscopy. The compounds were named acarviostatins III0(−1) and III23 according to the nomenclature of this group of metabolites. The two novel acarviostatins were both mixed noncompetitive inhibitors of porcine pancreatic <jats:italic>α</jats:italic>‐amylase (PPA). The inhibition constants (<jats:italic>K</jats:italic><jats:sub>i</jats:sub>) for acarviostatins III0(−1) and III23 were 0.009 and 0.026 μ<jats:sc>M</jats:sc>, respectively, 151 and 52 times more potent than acarbose.