We found new pentaamines, hexaamines and heptaamines which are aminobutyl derivative of homospermine (PA 444), in addition to four tetraamines, spermine (PA 343), thermospermine (PA 334), aminopropylhomospermidine (PA 344) and homospermine in extracts of the mature seeds of the vetch Vicia sativa by HPLC and GC. Two linear polyamines were identified as homopentamine [NH₂(CH₂)₄NH(CH₂)₄NH(CH₂)₄NH(CH₂)₄NH₂] (PA 4444) and homohexamine [NH₂(CH₂)₄NH(CH₂)₄NH(CH₂)₄NH(CH₂)₄NH(CH₂)₄NH₂] (PA 44444) by GC-mass analysis. Another eight tertiary branched polyamines were identified as N⁵-aminobutylhomospermine [NH₂(CH₂)₄N(NH₂(CH₂)₄)(CH₂)₄NH(CH₂)₄NH₂] [PA 4(4)44], N⁵-aminobutylhomopentamine [NH₂(CH₂)₄N(NH₂(CH₂)₄)(CH₂)₄NH(CH₂)₄NH(CH₂)₄NH₂] (PA 4(4)444), N¹⁰-aminobutylhomopentamine [NH₂(CH₂)₄NH(CH₂)₄N(NH₂(CH₂)₄)(CH₂)₄NH(CH₂)₄NH₂] [PA 44(4)44], N⁵,N¹⁰-bis(aminobutyl)homospermine [NH₂(CH₂)₄N(NH₂(CH₂)₄)(CH₂)₄N(NH₂(CH₂)₄)(CH₂)₄NH₂] [PA 4(4)4(4)4], N⁵-aminobutylhomohexamine [NH₂(CH₂)₄N(NH₂(CH₂)₄)(CH₂)₄NH(CH₂)₄NH(CH₂)₄NH(CH₂)₄NH₂] [PA 4(4)4444], N¹⁰-aminobutylhomohexamine [NH₂(CH₂)₄NH(CH₂)₄N(NH₂(CH₂)₄)(CH₂)₄NH(CH₂)₄NH(CH₂)₄NH₂] [PA 44(4)444], N⁵,N¹⁰-bis(aminobutyl)homopentamine [NH₂(CH₂)₄N(NH₂(CH₂)₄)(CH₂)₄N(NH₂(CH₂)₄)(CH₂)₄NH(CH₂)₄NH₂] [PA 4(4)4(4)44] and N⁵,N¹⁵-bis(aminobutyl)homopentamine [NH₂(CH₂)₄N(NH₂(CH₂)₄)(CH₂)₄NH(CH₂)₄N(NH₂(CH₂)₄)(CH₂)₄NH₂] [PA 4(4)44(4)4].