Water remediation utilizing sorption has found strong interest due to its inexpensiveness, universal nature and ease of operation. In particular, thermo-responsive sorbents consisting of N-isopropylacrylamide (NIPAAm) offer significant potential as “smart” and advanced materials to remove multiple aqueous pollutants. NIPAAm exhibits excellent thermo-responsiveness, which senses the external temperature variation and changes its swelling and sorption behaviors in a sharp and rapid manner. At the beginning of this work, an extensive review of literature has been compiled to provide a summary of NIPAAm-based thermo-responsive sorbents in water/wastewater remediation applications. Initially, we developed a novel approach to synthesize and characterize NIPAAm copolymeric hydrogels. Four different polyphenolic crosslinkers including curcumin multiacrylate (CMA), quercetin multiacrylate (QMA), 4,4’-dihydroxybiphenyl diacrylate (44BDA) and chrysin multiacrylate (ChryMA) were successfully incorporated into crosslinked hydrogels. Their temperature responsiveness and lower critical solution temperature (LCST) were characterized using swelling studies and differential scanning calorimetry (DSC). Increasing the crosslinker content resulted in a significant decrease in the swelling ratio and LCST, which was due to the increased crosslinking and hydrophobicity introduced by the polyphenolic crosslinkers. We also demonstrated the application of two sets of aforementioned crosslinked hydrogels (NIPAAm-co-CMA and NIPAAm-co-44BDA) as effective gel sorbents to capture phenol as a model contaminant. Temperature-dependent sorption was evaluated through a binding study of phenol at 10°C and 50°C. Significant enhancement in the sorption was observed at 50°C, and this can be attributed to the phase transition induced hydrophobic interactions between the copolymer gel and phenol. Moreover, the obtained hydrogels possessed facile and efficient regeneration ability in water at 10°C, without requiring harsh solvent treatment or high energy input. Building on the sorption behavior observed with crosslinked NIPAAm hydrogels, we extended the investigation to linear copolymer systems, and these were demonstrated as a temperature responsive flocculants. Here, NIPAAm copolymers consisting of 2-phenylphenol monoacrylate (2PPMA) were successfully developed as smart flocculants to remove metal oxide nanoparticles (e.g., Fe3O4, CeO2, TiO2). The incorporation of 2PPMA enhanced the flocculation at temperatures above the LCST (e.g., 50°C), which was due to the combined hydrophobicity of 2PPMA and NIPAAm. Overall, NIPAAm-based sorbents have a variety of applications in aqueous pollutant removal and are a promising class of materials for cost-effective water remediation technology.