Treatment of 2,2′-diacetoxy-1,1′-binaphthyl-6,6′-bis(ethyne), L-H 2 , with one equiv of trans-Pt(PEt 3 ) 2 Cl 2 led to a mixture of different sizes of chiral metallocycles [trans-(PEt 3 ) 2 Pt(L)] n (n=3–8, 1–6). Each of the chiral molecular polygons 1–6 was purified by silica-gel column chromatography and characterized by 1 H, 13 C{ 1 H}, and 31 P{ 1 H} NMR spectroscopy, MS, IR, UV–Vis, and circular dichroism (CD) spectroscopies, size exclusion chromatography, and microanalysis. Chiral molecular square 2 was also characterized by single-crystal X-ray diffraction. The acetyl groups of 2 were readily deprotected under mild conditions to generate 2a which possesses exposed chiral dihydroxy functional groups. The dihydroxy groups were functionalized with n-octadecyl chains or Fréchet-type dendrons to generate dendritic molecules built on a chiral molecular square core. This work shows the potential of generating interesting functional supramolecular systems based on Pt-alkynyl chiral molecular polygons.