X-ray crystal structures are reported for five silver(I) complexes of four monoterpenoid alkenes. Discrete mononuclear complexes of the chiral alkenes (1S)-(-)-α-pinene and (1S)-(-)-ß-pinene with silver perchlorate and silver hexafluorophosphate are described. The achiral diene γ-terpinene forms a discrete mononuclear adduct with silver hexafluorophosphate and a two-dimensional polymeric network structure with silver triflate. The chiral diene (R)-(+)-limonene forms a one-dimensional chiral coordination polymer with silver hexafluorophosphate. In all structures the silver atom is η2-bonded to the carbon–carbon bond(s) of the monoterpene with slightly longer bond distances to the more substituted carbon of the alkene moiety.