In this study, G5 PAMAM dendrimer and alpha-, beta-, gamma-cyclodextrin (CD) conjugates were synthesized. Host-guest behaviors of the conjugates toward five guest molecules including sodium methotrexate (MTX), amantadine hydrochloride (ADH), sulfamethoxazole (SMZ), sodium deoxycholate (SDC), and sodium dodecyl sulfate (SDS) were analyzed by NOE NMR techniques. Among the five guest molecules, ADH only binds with beta-CD in G5-beta-CD, SDC shows higher priority to localize within the cavity of gamma-CD in G5-gamma-CD, while MTX exhibits selective encapsulation within the cavities of G5 dendrimer in G5-alpha-CD. SDS has high binding affinity with alpha-CD in G5-alpha-CD but forms a precipitate in the complex solution. SMZ shows simultaneous encapsulation within CDs (alpha-, beta-, and gamma-CD) or G5 in the presence of the three conjugates. The host behavior of G5-CD conjugates depends on CD cavity size, guest size, and hydrophobicity. The results obtained in this study are helpful in the optimization of dendrimer-CD conjugate-based drug delivery systems.