Molecular recognitions, causing supramolecular complex formation between a hyperbranched polymer molecule (polyamidoamine (PAMAM) dendrimer generation 3) with oppositely charged surfactant sodium dodecyl sulfate (SDS) in aqueous solution, were studied by using various spectroscopic techniques and calorimetric titration of heat change measurements. Spectroscopic measurements were performed using dynamic Stokes shift (DSS), rotational anisotropy decay, and translational diffusion of a fluorescent probe molecule coumarin 153 (C153) noncovalently attached to the dendrimer-surfactant complex. All these studies unanimously confirm that the critical aggregation concentration (CAC) of SDS falls to similar to 0.8 mM (from its critical micelle concentration (CMC) similar to 8 mM) in the presence of similar to 0.2 mM dendrimer. Further studies of isothermal titration calorimetry (ITC) measurement show that the CAC of SDS in the presence of dendrimer remains invariant to the dendrimer concentration. Complexation reaction between SDS and dendrimer is highly exothermic in nature. A maximum heat release (Delta H similar to -6.6 kJ/mol of SDS binding) was observed at a SDS-to-dendrimer mole ratio of similar to 3-5; where up to 3 to 5 SDS molecules were encapsulated by one dendrimer molecule to form dendrimer-SDS encapsulation complex. When negatively charged SDS was replaced with a positively charged surfactant dodecyl-trimethylammonium-bromide (DTAB), we found that the DTAB hardly interacted with positively charged dendrimer due to the charge-charge repulsions.