<jats:title>Abstract</jats:title><jats:p>Three unique metabolites, namely, phomopsis‐H76 A (<jats:bold>1</jats:bold>), B (<jats:bold>2</jats:bold>), and C (<jats:bold>3</jats:bold>), were isolated from the mangrove endophytic fungus <jats:italic>Phomopsis</jats:italic> sp. (#zsu‐H76). Structures were determined by spectroscopic methods, mainly 1D and 2D NMR spectroscopy. Compound <jats:bold>1</jats:bold>–<jats:bold>3</jats:bold> are all dimers. Compounds <jats:bold>2</jats:bold> and <jats:bold>3</jats:bold> possesses a pyrano[4,3‐<jats:italic>b</jats:italic>]pyran‐5(2<jats:italic>H</jats:italic>)‐one ring system that is unprecedented in nature. Primary bioassays showed that <jats:bold>1</jats:bold> accelerated the growth of subintestinal vessel plexus (SIV) branch markedly, whereas <jats:bold>3</jats:bold> showed inhibition of SIV. Compounds <jats:bold>1</jats:bold>–<jats:bold>3</jats:bold> showed no activity in antibacterial and cytotoxic tests.