Polymeric microgels were prepared from dextran (Dex) by crosslinking linear natural polymer dextran with divinyl sulfone (DVS) with a surfactant-free emulsion technique resulting in high gravimetric yield of 78.5 +/- 5.3% with wide size distribution. Dex microgels were chemically modified, and then used as catalyst in the methanolysis of NaBH4 to produce H-2. The chemical modification of Dex microgel was done on epichlorohydrin (ECH)-reacted Dex microgels with ethylenediamine (EDA), diethylenetriamine (DETA), and triethylenetetraamine (TETA) in dimethylformamide (DMF) at 90 degrees C for 12 hours. The modified dextran-TETA microgels were protonated using treatment with hydrochloric acid (HCl) and m-Dex microgels-TETA-HCl was found to be a very efficient catalyst for methanolysis of NaBH4 to produce H-2. The effects of reaction temperature and NaBH4 concentration on H-2 generation rates were investigated and m-Dex microgels-TETA-HCl catalyst possessed excellent catalytic performances with 100% conversion and 80% activity at end of 10 consecutive uses and was highly re-generatable with simple HCl treatment. Interestingly, m-Dex microgels-TETA-HCl catalyst can catalyze NaBH4 methanolysis reaction in a mild temperature range 0 to 35 degrees C with Ea value of 30.72 kJ/mol and in subzero temperature range, -20 to 0 degrees C with Ea value of 32.87 kJ/mol, which is comparable with many catalysts reported in the literature.