Microgels of polymeric ionic liquid (PIL) combine the advantages of the both ionic liquids and polymeric microgels. The microgel in this work was prepared from 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) treated with tris(dioxa-3,6-heptyl) amine (TDA-1) (p(AMPS)-TDA-1), synthesized in a water in oil micro-emulsion via photo-irradiation, with a wavelength of 420nm, for 2h. The synthesized p(AMPS)-TDA-1 PIL microgels were then characterized via microscope, scanning electron microscope, Fourier transform infrared spectrometer, thermogravimetric analyzer, and zeta potential measurements. Applications of these PIL microgels were also investigated by using p(AMPS)-TDA-1 PIL as a template for in situ Co and Ni metal nanoparticle preparation and as a catalyst in the hydrolysis of NaBH4 for H-2 production. The potential for p(AMPS)-TDA-1 PIL microgels as metal-free catalyst in the methanolysis of NaBH4 for H-2 generation was explored as well. It was found that the metal-free p(AMPS)-TDA-1 PIL microgel displayed superior catalytic activity in methanolysis of NaBH4 reaction with a hydrogen generation rate (HGR) of 854 +/- 51.6mL H-2/(ming of catalyst) and very low activation energy (E-a), 14.3kJ/molE(a). Reusability tests on the p(AMPS)-TDA-1 PIL microgel as a metal-free catalysis showed promising results; At end of the 10th trail, no decrease in the 100% conversion was observed with only 14% decrease in activity.