Porous coordination polymers (PCPs) are an excellent class of porous crystalline materials with tunable properties and intriguing potential applications spanning multiple disciplines. In this work, we report the synthesis and characterization of a PCP (HI‐103) based on 4,4’‐dithiodibenzoic acid ligand and zinc nitrate with two DMF molecules residing in the porous network. The stability of the porous network was analyzed by heating the compound at 60.0 °C for two days, and the structural analysis revealed a new PCP (HI‐104) was formed with one of the DMF molecules, indicating a single‐crystal to single‐crystal (SCSC) transformation. The solvent molecules were completely removed by extensive drying (HI‐103‐dry), and the integrity of the porous network was verified by powder X‐ray diffraction (PXRD) and thermogravimetric analysis. The reversibility of SCSC transformation was confirmed by treating HI‐103‐dry with DMF molecules, resulting in HI‐103 after five days. The adsorption studies of HI‐103‐dry with other solvents revealed that SCSC transformation was not observed for DMA and DEA, but some structural changes were observed in the presence of DMSO. The adsorption studies performed in the presence of an equimolar mixture of DMF, DMA, and DMA indicated that HI‐103‐dry could selectively adsorb DMF molecules from the analogous mixture.