The naturally occurring octacyclopeptide brachystemin F was synthesized for the first time in the present study by a two-step solid-phase/solution strategy. All the amino acids in this study have the L-configuration. The linear octapeptide was assembled by standard Fmoc solid-phase peptide synthesis (SPPS), and subsequent cyclization was carried out by the solution method. The target compound was purified by preparative RP-HPLC, and its structure was identified by H NMR, C NMR, and MS. [ABSTRACT FROM AUTHOR]