The　integration　of　anionic　Ti4L6　(L　=　embonate)　cages　and　pi-conjugated　coordination　cations　into　ordered　structures　can　produce　high-performance　nonlinear　optical　(NLO)　materials.　More　specifically,　by　employing　Ti4L6　cages　for　assembly　with　mixed　N,N-chelated　and　P,P-chelated　type　conjugated　organic　ligands　and　Ag+　ions,　three　cage-based　structures　have　been　synthesized　and　structurally　characterized.　Among　them,　an　ion　pair　structure　with　strong　pi-pi　accumulation　exhibits　a　significant　third-order　NLO　response,　and　an　excellent　optical　limiting　effect　has　been　experimentally　verified.　This　work　provides　a　promising　material　for　NLO　applications.