The compound [(Nb₆O₁₉)@Ag₃₄(^tBuCC)₂₄(CH₃COO)₂] (Ag₃₄) was synthesized using the solvothermal method combined with volatilization. This was the first case, to the best of our knowledge, of isolating a silver cluster containing a polyoxoniobate (PONb) template. The luminescence, solution behavior and solid-state stability of Ag₃₄ were studied in detail. Electrospray ionization mass spectrometry indicated that Ag₃₄ can maintain the integrity of its skeleton in solution. Detection of temperature could be a potential application of its unique luminescent behavior. We expect this work to inspire further fabrications of PONb-templated high-nuclearity silver clusters.