For the interlayer dielectric in microelectronics, light element compounds are preferably accepted due to less electronic polarization. Here, the nontrivial dielectric nature of the Sb 4 O 6 cage-molecular crystal, known as α-antimony trioxide (α-Sb 2 O 3 ), is reported. The gas-phase synthesized α-Sb 2 O 3 nanoflakes are of high crystal quality, from which the abnormal local admittance responses were revealed by scanning microwave impedance microscopy (sMIM). The remarkably low dielectric constant (k), 2.0∼2.5, is corroborated by the analysis of the thickness-dependent sMIM-capacitance signal. In light of the theoretical calculations, the ultralow molecular density and the significantly suppressed ionic polarization are both crucial to the highly reduced k. Combining with the excellent optical band gap, thermal stability, and breakdown strength, α-Sb 2 O 3 is a promising low k dielectric. KEYWORDS: low k, α-Sb 2 O 3 , Sb 4 O 6 cage, molecular crystal, interlayer dielectric