Stereochemically homogeneous and architecturally discrete isotactic-atactic-isotactic tri-block stereoblock PP (sbPP) thermoplastic elastomers in which the block lengths for each domain type can be varied in programmed fashion while keeping total molecular weight and molecular weight polydispersity the same has been achieved for the first time. Five sbPP materials were prepared: sbPP-1 (6iso-88a-6iso), total isotactic content, 12%; sbPP-2 (12iso-76a-12iso), 24%; sbPP-3 (18iso-64a-18iso), 36%; sbPP-4 (24iso-50a-26iso), 50%; and sbPP-5 (20iso-64a-33iso), 53%. All five sbPP materials were successfully processed by solution-based electrospinning to provide fiberous mats with feature sizes on the nanometer to micrometer length scale. Extensive characterization by analytical (SEM, AFM, tensile testing, DSC,), spectroscopic (FT-IR, FT-Raman), and synchrotron X-ray diffraction techniques of bulk samples, electrospun fibers and solvent cast films of the sbPP samples revealed well-defined trends in elastic properties, morphologies and crystallinity that are associated with a higher degree of crystallinity that emerges with higher isotactic contents. The results of these investigations serve to provide an important foundation that can be used to potentially identify the best combination of stereoerror level incorporation within the isotactic domains and total isotactic content for these architecturally discrete sb-PP materials for maximizing desirable elastomeric traits and solution-based (electrospinning) processing methodology with the goal of achieving the best possible structural forms for potential product applications.