Two new hyper-crosslinked polymers (HCPs), denoted as TCDI-PVA and CDI-PVA are obtained and applied in I-2 adsorption. Due to their porous structures and interactions between N, S heteroatoms and I-2, Both HCPs possess ultrahigh uptake capacities in I-2 vapor (5.9 g/g for TCDI-PVA, 3.5 g/g for CDI-PVA). The mechanistic studies confirmed that both the porous structures and the introduction of heteroatoms (N, S) in HCPs account for positive effects for I-2 uptake.