A　series　of　new　mononuclear　and　dinuclear　copper(i)　triphenylphosphine　complexes　with　functionalized　3-(2′-pyrimidinyl)-1,2,4-triazole　ligands　have　been　synthesized　and　characterized,　in　which　functionalized　3-(2′-pyrimidinyl)-1,2,4-triazole　adopts　neutral　mono-　and　bis-chelating　coordination　modes　and　a　mono-anionic　bis-chelating　binding　manner　due　to　the　1,2,4-triazolyl-NH　deprotonation.　All　these　Cu(i)　complexes　display　a　relatively　weak　low-energy　absorption　in　a　CH2Cl2　solution,　ascribed　to　the　charge-transfer　transitions　with　appreciable　MLCT　character,　as　suggested　by　TD-DFT　analyses.　These　Cu(i)　complexes　are　all　emissive　in　solution　and　in　the　solid　state　at　ambient　temperature,　and　their　luminescence　properties　can　be　well　modulated　via　the　addition　of　the　second　{Cu(PPh3)2}　unit　and　modification　of　3-(2′-pyrimidinyl)-1,2,4-triazole　involving　the　N-H　deprotonation　and　the　substituent　variation　of　the　1,2,4-triazolyl　ring.　It　is　also　demonstrated　that　introducing　the　trifluoromethyl　group　into　the　1,2,4-triazolyl　ring　is　helpful　for　enhancing　the　solid-state　luminescence　properties　of　the　1,2,4-triazole-based　Cu(i)　complexes,　whereas　the　introduction　of　the　tert-butyl　group　into　the　1,2,4-triazolyl　ring,　the　1,2,4-triazolyl-NH　deprotonation,　and　the　use　of　the　pyrimidinyl　ring　instead　of　the　pyridyl　ring　are　all　unfavorable.　©　2017　The　Royal　Society　of　Chemistry.