In situ Raman spectroscopic studies have been carried out on Ag3[Co(CN)6] at high pressures up to 16 GPa. From the pressure dependence of the Raman frequencies, the mode Grüneisen parameters in the trigonal and the monoclinic phases are obtained. Besides the reported trigonal-to-monoclinic transition at 0.2 GPa, it is observed that the compound shows pressure-induced amorphization above 13 GPa. The recovered sample shows features characteristic of amorphous carbon nitride, indicating the decomposition of the parent compound in the pressure-reducing cycle. Temperature dependence of the mode frequencies over the range 80–290 K is also investigated, from which the modes that are more anharmonic than other modes are identified.