The　integration　of　the　rich　electronic　properties　of　3d-4f　heterometallic　clusters　with　rigid　and　diamagnetic　polyoxometalates　is　of　great　interest　and　is　expected　to　yield　novel　materials　with　enhanced　properties　due　to　synergistic　effects.　For　the　first　time,　the　study　succeeds　in　introducing　fluorescent　Zn-Ln　heterometallic　clusters　into　polyoxoniobates　(PONbs),　forming　a　family　of　rare　giant　heterometallic　PONbs　with　various　architectures,　including　78-metal　{Zn10Eu8Nb60},　112-metal　{Zn16Ln8Nb88}　(Ln　=　La,　Y),　and　165-metal　{Na2Zn29Ln12Nb122}　(Ln　=　Pr,　Nd,　Sm,　Eu,　Gd,　Tb,　Dy,　Ho).　These　heterometallic　PONbs　exhibit　many　appealing　structural　features　and　unique　building　blocks.　Particularly,　they　are　the　largest　3d-4f　heterometallic　PONbs　and　also　the　PONbs　incorporating　the　largest　number　of　3d-4f　metal　ions　and　the　highest-nuclearity　3d-4f　clusters　known　to　date.　Furthermore,　the　combination　of　PONbs　and　Zn-Ln　clusters　renders　these　new-type　heterometallic　PONbs　multicolor　luminescent　characteristics　and　high　fluorescence　quantum　yields,　making　them　promising　candidate　cluster　molecules　for　responsive　photonic　barcodes.