The PEI microgels were synthesized by micro-emulsion polymerization technique, and protonated with 0.1 M HCl acid treatment due the existence of abundant number of tertiary, secondary and primary amine groups on the PEI network. Then, the protonated PEI microgels (Q-PEI) were exposed to anion exchange reaction with differ ionic liquid forming salts, such as with sodium dicyanamide (SDCA), ammonium hexafluorophosphate (AHFP), and sodium tetrafluoroborate (STFB) in aqueous medium for the preparation of PEI-based ionic liquid colloidal microgels. Finally, the anion exchanged PEI based ionic liquid colloids (ILCs) were used as template for in situ metal nanoparticles preparation such as Co, Ni, and Cu to generate ILC composite (PEI-M) (M: Co, Ni, and Cu). Then, PEI-M composites were used in hydrolysis of NaBH4 for H-2 generation. Various parameters affecting the H-2 production rate such as the metal types, and the temperature were investigated, and the activation parameters were evaluated. Additionally, PEI-M metal composites were also shown to very effective catalyst in reduction of 4-nitophenol (4-NP) to 4-aminophenol (4-AP). (C) 2015 Elsevier B.V. All rights reserved.