In this work, we provide a facile and valid one-pot synthesis method to create unreported hierarchical cluster of lanthanide cluster plus gold cluster (Ln-Au cluster), by introducing the ligands with bifunctional groups of carboxyl and sulfhydryl. The identities of Ln-Au clusters are fully characterized to be Ln7Au20 (MPCA)21 (Ln = Ce, 1; Eu, 2; Tb, 3; MPCA = 2-mercaptonicotinic acid) and Ln5Au18(TSA)15 (Ln = Ce, 4; Eu, 5; Tb, 6; TSA = thiosalicylic acid). Results reveal the six Ln-Au clusters are hierarchical structure that Ln cluster and Au cluster are connected by bifunctional ligands of MPCA or TSA. The excellent “antenna effect” of TSA results in highly luminescence quantum yield of 67% for 6. Interestingly, Ln-Au clusters 4 and 5 show very high MB adsorption capacity of 189 and 158 mg/g in short adsorption equilibrium time of 30 and 5 min, respectively.