As common coinage metals, silver and silver compounds have very rich application in the organic catalytic reaction. Immobilization of silver compounds on heterogeneous media is the most common way used in industrial catalytic reactions. In this work, we designed and synthesized a new heterogeneous porous silver catalyst, with in situ-formed Ag-S rods as connecting nodes and thiosemicarbazide-functionalized linear ligands, used in both σ- and π-catalytic transformations. Strong Ag-S bonds bypassed the loss of noble silver elements and inhibited the formation of nonporous silver particles which always led to the decrease of yields in homogenous reactions. Furthermore, various derivatives of propargylamines and phenylacetylenes were applied as both σ and π-active substrates with moderate to good yields.