The conformational and polymorphic transformations in the melt-spun monofilament of syndiotactic polypropylene upon annealing and subsequent stretching have been first explored by micro-FTIR studies. The results indicate that annealing of as-spun monofilament gives rise to an unusual increase in the molecular orientation of helical conformations in both amorphous phase and ordered crystals as a result of structural transitions of transplanar conformations to helical ones as well as mesophase to ordered crystals. The increased molecular orientation in the annealed monofilament is mainly responsible for the enhanced strength during stretching. Furthermore, high stress exerted by the molecular chains of annealed monofilament is confirmed by the significant structural transitions opposite to that induced by annealing.