Benefit　from　the　strong　coordination　property,　lanthanide　metal　ions　have　been　used　as　competitive　reagents　to　modulate　the　fluorescence　changes　of　the　system.　However,　lanthanide　metal　ions　as　inducers　for　aggregation-induced　emission　enhancement　in　nanosystems　is　rare.　Herein,　we　report　a　＇turn　on–off-on＇　fluorescent　switch　for　cascade　detection　of　acid　phosphatase　(ACP)　and　adenosine　triphosphate　(ATP)　based　on　the　competitive　coordination　of　samarium　ions　(Sm3+).　Novel　copper　nanoclusters　(CuNCs)　with　long　wavelength　emission　(614 nm)　stabilized　by　glutathione　(GSH)　and　glycylglycine　(Gly-Gly)　have　been　confirmed　to　have　AIE　property.　With　the　continuous　aggregation　of　GSH/Gly-Gly　CuNCs　under　the　induction　of　Sm3+,　the　fluorescence　of　the　system　increased　to　achieve　the　＇turn-on＇　process.　The　coordinated　behaviour　between　Sm3+　and　GSH/Gly-Gly　CuNCs　is　discussed.　Due　to　the　strong　metal　coordination　ability　of　ATP,　the　Sm3+　coordinated　with　the　GSH/Gly-Gly　CuNCs　is　competed　out,　resulting　in　the　fluorescence　＇turn-off＇　process　of　the　system.　As　the　substrate　of　enzymatic　hydrolysis　of　ACP,　with　the　continuous　hydrolysis　of　ATP　by　ACP,　Sm3+　coordinates　with　GSH/Gly-Gly　CuNCs　again,　which　leads　to　the　AIE　effect　and　realize　the　fluorescence　＇turn-on＇　process　of　the　system.　This　strategy　results　in ATP　linear　range　of　0.508　~　120.0 μM　with　a　detection　limit　of　0.508 μM　(S/N　=　3)　and　ACP　linear　range　of　0.011　~　30.0　U·L−1　with　a　detection　limit　of　0.011　U·L−1　(S/N　=　3).　Application　to biologic　samples　was successful.　Graphical　Abstract:　[Figure　not　available:　see　fulltext.].　©　2023,　The　Author(s),　under　exclusive　licence　to　Springer-Verlag　GmbH　Austria,　part　of　Springer　Nature.