The present paper deals with the formation and detailed characterization of the gamma-cyclodextrin (gamma-CD) inclusion compounds (ICs) formed with two different high molecular weight isotactic polyolefins, i.e., polypropylene (i-PP) and poly(butene-1) (i-PB). Wide-angle X-ray diffraction (WAXD), differential scanning calorimetry (DSC), solid-state C-13 NMR, and FT-infrared (FTIR) observations were used to prove the inclusion of the guest polymer chains into the narrow channels provided by the stacks of the doughnut-shape CD molecules. The main aim of polyolefin inclusion into a solid host lattice like gamma-CD is to extend and reorganize their conformations, with the hope of improving their commercial properties following their coalescence from their ICs. In the second part of the paper, both coalesced i-PP and i-PB obtained after the host gamma-CD is removed reveal different characteristics as compared with the as-received or corresponding control samples.