The beneficial effect of the bifunctional character of the chitosan@titania hybrid in heterogeneous catalysis was elucidated: considering a prototypical Henry condensation, Michael addition, and Jasminaldehyde synthesis, the cohabitation of a basic site (NH(2)) and an acidic site (Ti) in the same reactor provided clear activity and selectivity enhancements, with respect to the monofunctional acidic titania and basic chitosan counterparts.