AbstractWhereas its renewable source, vegetal carbon will trend more and more to be considered as a starting raw material for organic synthesis. Although cellulose is proportional the first in volume, starch shows the most industrial development to versatile polymers and molecules due to chemical and biochemical conversions. However, chemistry of saccharides and polyols is made tedious because of the polyfunctionality. This last point leads to a specific reactional strategy built up with protection of reactional groups. Time‐consuming and uneconomical steps have sometimes dissuaded industrial researchers from developing new molecules. So, development of new synthetic routs and catalysts with specific separation tools will open the door to a new generation of products comming from sucrochemistry, with better yields and improved selectivity. In order to illustrate this new way, acetalisation of sorbitol with benzaldehyde has been chosen. An inverse phase transfer catalysis (PTC) is used and comparison with a traditional catalysis is made. After reviewing different operational factors, emphasize is put on the highest selectivity obtained with a PT