Natural fiber-reinforced polymers or biocomposites are becoming increasingly popular as an environment friendly alternative to traditional glass fiber-reinforced thermoplastics. The mechanical properties of reinforced biocomposites, such as flax/polylactic acid (PLA), are largely governed by the level of interfacial interactions between the two constituents apart from their intrinsic properties. The hierarchical organization of various polysaccharides present in natural fibers results in complex mechanisms at the interface which are still poorly understood and difficult to analyze through a traditional approach that rely on indirect assessments. The possibility of measuring direct adhesion force between individual particles using the colloidal force microscopy has been exploited here by developing an experimental set-up in which a micrometer colloidal PLA bead is brought into close contact with molecularly smooth polysaccharide surfaces that mimic the main constituents of flax fibers, cellulose, hemicellulose, and pectins. Adhesion force measurements performed under ambient and low relative humidity conditions indicate that cellulose/PLA is the weakest interface in the biocomposite. Moreover, the results emphasize the important role of water molecules for the more hydrophilic polymers in flax fibers that takes place in the fundamental forces involved in the adhesion phenomena at the biocomposite interface.