Quantitative production of 2,5-bis(hydroxymethyl) furan (BHMF) was achieved at room temperature (25 degrees C) via highly selective hydrogenation of biomass-derived 5-hydroxymethylfurfural (HMF) employing alkali salt KF as catalyst and polymethylhydrosiloxane (PMHS) as hydrogen source. A moderate turnover frequency (TOF: 4.2 h(-1)) was observed for this mild and sustainable reaction process. Moreover, a combination of Amberlyst-15 with KF could successfully catalyze the direct synthesis of BHMF from hexose sugars such as fructose and inulin via tandem dehydration and hydrogenation in a single pot. This catalytic system is more selective compared with H-2-participated counterpart, giving a high BHMF yield and selectivity of up to 98% and > 99% from HMF, respectively. Moreover, the catalytic performance of KF could remain for at least five consecutive cycles in the conversion of HMF to BHMF.