2-Biphenylethyl and 2-biphenylhexyl-terminated polyhedral oligomeric octasilicate (OS)-core polyester-typed dendrimers, denoted as OS-C2-BP and OS-C6-BP, respectively, were prepared by ring-opening reaction and subsequent condensation of octakis(propenyl succinicanhydrido)polyhedral octasilicate (OS-SA) with 2-(4-phenylphenoxy)ethanol (BP-C2-OH) and 6-(4-phenylphenoxy)hexanol (BP-C6-OH), respectively. OS-C2-BP formed a transparent film, whereas OS-C6-BP formed an opaque whitish waxy film. The coating film of OS-C2-BP was easily peeled off from a substrate and formed a free-standing film. The results of X-ray diffraction and differential scanning calorimeter suggest that the film of OS-C2-BP was amorphous, whereas OS-C6-BP contained crystalline domains. Thermogravimetric analysis of OS-C2-BP and OS-C6-BP showed 5 wt % weight losses at 362 degrees C and 283 degrees C, respectively. OS-C2-BP offered higher thermal resistance than OS-C6-BP. (c) 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 1437-1443