Ca-Na ordering and structural polarity of subcells in an intermediate plagioclase with modulated structure have been observed using Z-contrast imaging with an aberration-corrected scanning transmission electron microscope. Neighboring lamellar domains with I1 symmetry are related by inversion twin operation, instead of anti-phase domain boundaries (or APBs) as in all previously reported structure models. The boundaries between lamellar domains have I1̄ symmetry instead of C1̄ symmetry. Modulated plagioclase has unique Ca-Na and Al-Si ordering structure that is different from those in end-member structures of anorthite and low albite. The modulated structures of intermediate plagioclase are not metastable structures formed during phase transition, but instead thermodynamically stable structures at low temperature due to Ca-Na ordering within the subcells with I1 symmetry.