Interactions among HMHEC (hydrophobically modified hydroxyethyl cellulose) and between HMHEC and amylose were investigated by means of dynamic force spectroscopy of single molecular pairs. The technique was realized using a scanning probe based platform, and the molecular pair interactions were investigated in aqueous solutions over a range of force loading rates. Both hydrophobic interactions among hydrophobe C(16) alkyl side chains in HMHEC and association between these hydrophobes in HMHEC and amylose showed a stretching type peak. The distribution analysis of rupture force based on Bell-Evans's model revealed that the peaks had a most probable rupture force ranging from 27 pN at a force loading rate r(f) = 0.43 nN/s to 125 pN at r(f) = 170 nN/s for HMHEC-HMHEC, and from 13 pN at r(f) = 0.20 nN/s to 34 pN at r(f) = 33.7 nN/s for HMHEC-amylose interactions. The distance of the energy barrier relative to the minimum, x(beta), and the apparent lifetime in the absence of external force, tau, were found to depend on the force loading rate, and the average values are estimated to be 0.99 nm and 0.89s for HMHEC-HMHEC and 0.31 nm and 0.075s for HMHEC-amylose interactions. The obtained data for these pairwise molecular interactions are underpinning the associative behavior of the macroscopic properties of aqueous solutions of these polysaccharides.