<jats:p>Four new nanaomycins (<jats:bold>1</jats:bold> – <jats:bold>4</jats:bold>), together with two known compounds, nanaomycin <jats:italic>α</jats:italic>A (<jats:bold>5</jats:bold>) and nanaomycin <jats:italic>β</jats:italic>A (<jats:bold>6</jats:bold>) were isolated from a fermentation broth of <jats:italic>Streptomyces hebeiensis</jats:italic> derived from lichen. The structures of the new nanaomycins <jats:bold>1</jats:bold> – <jats:bold>4</jats:bold> were established using comprehensive <jats:styled-content style="fixed-case">NMR</jats:styled-content> spectroscopic data analysis as well as <jats:styled-content style="fixed-case">UV</jats:styled-content>,<jats:styled-content style="fixed-case"> IR</jats:styled-content>, and <jats:styled-content style="fixed-case">MS</jats:styled-content> data. The antimicrobial activities of <jats:bold>1</jats:bold> – <jats:bold>6</jats:bold> were evaluated against <jats:italic>Gram</jats:italic>‐positive bacteria and fungus. Compounds <jats:bold>5</jats:bold> and <jats:bold>6</jats:bold> showed antimicrobial activities against the test microorganisms, while <jats:bold>1</jats:bold> – <jats:bold>4</jats:bold> were inactive at 100 μg/ml.