The larynx is an important organ of human speech, and patients with laryngeal cancer may face great pain of losing their functions. For the prevention and therapy of laryngeal carcinoma, two new Zn(II)/Cd(II) coordination polymers, namely [Zn3(L)2(4,4′-bipy)]n·2n(DMF) (1) and [Cd3(L)2(bpp2)n·2n(H2O)·2n(DMF) (2) (H3L = 4,4′,4′′-ticarboxytriphenylamine, 4,4′-bipy = 4,4′-bipyridine, bpp = 1,3-bis(4-pyridyl)propane, DMF = N,N-dimethylformamide), were prepared. The treatment and protection activity of the new compounds against the laryngeal carcinoma was evaluated in this research, and the corresponding mechanism was explored at the same time. Firstly, CCK-8 assay was conducted to measure the inhibitory activity of compounds on the viability of laryngeal carcinoma cells. Additionally, the expression of miR-223-3P in MSC exosomes was also measured by real time RT-PCR assay.