A tandem catalyst system comprised of trifluoromethanesulfonic (triflic acid, HOTf) or Hafnium tetratriflate (Hf(OTf)4) and Ru/C in glacial acetic acid (HOAc) as the solvent at 200 °C and ~ 7 MPa hydrogen pressure in a batch reactor converts penta‐acetyl‐xylitol ((2R,3R,4S)‐Pentane‐1,2,3,4,5‐penta‐acetoxy‐pentane) or unprotected xylitol to 3‐acetoxymethylene‐tetrahydrofuran (3‐AMT) in up to 15 % yield at full conversion. A comparative analysis by SEM‐EDS and XPS of the fresh commercial Ru/C catalyst vs catalyst reused and recovered after 5 cycles shows increasing aggregation of ruthenium to larger particles with a concomitant decrease in yield of 3‐AMT to 8‐9 % for cycles 4 and 5. 3‐AMT or its hydrolysis product 3‐hydroxymethyl‐tetrahydrofuran (3‐HMT) are valuable synthons for the preparation of agrochemicals, pharmaceuticals and specialty polyurethanes and polyesters.