The oppositely oriented lamellae in ridge and valley bands of ring-banded spherulites in biodegradable poly(3-hydroxybutyric acid-co-3-hydroxyvaleric acid) (PHBV) interacting with amorphous poly(vinyl acetate) (PVAc) were examined using polarized-light optical, scanning electron, and atomic-force microscopy techniques (POM, SEM, AFM). Solvent-etching and fracturing were utilized for probing the interior morphology of the large-size ring-banded spherulites in PHBV/PVAc (70/30) blend [T(c) = 110 °C] films or thick bulk of various thicknesses. SEM analysis revealed that dual ridges of two opposite-oriented lamellae correspond to two-color bands (yellow and blue) of successive rings in POM micrographs. Fracture of thick blend samples further exposed that interior 3D spherulites were composed of sheath-kebab (similar to corrugated board) lamellae of two mutually perpendicular orientations.