In this study, changes in the molecular structure of a sheath-core polyethylene (PE)/polypropylene (PP) bicomponent monofilament were investigated using different fractions of sheath or core components. The melt complex viscosity of sheath PE showed a greater shear thinning behavior than core PP. For both as-spun and drawn filaments, the crystal structure of sheath PE developed better than that of core PP. In the as-spun monofilament, the core PP crystal structure did not develop well, while sheath PE showed a more developed crystal structure. Further, sonic velocity indicating the molecular orientation increased upon drawing but was rarely dependent on the sheath PE fraction for both as-spun and drawn monofilaments.