The p-phenylenedialdehyde mono-acetal was prepared by the reaction of p-phenylenedialdehyde with acetic anhydride in the presence of InBr₃. The calix[4]resorcinarene was prepared using the p-phenylenedialdehyde mono-acetal and resorcinol as starting materials. By pestling pentaerythritol and calix[4]resorcinarene, and then pestling the intermediate and 3-[4-(dioxolan-2'-yl)phenyl]-9-(4-diacetoxymethyl)phenyl-2,4,8,10-tetraoxaspiro[5.5]undecane, the calix[4]resorcinarenes star compound was synthe- sized under a solvent-free condition. After the pestling, the mixture was washed with water and recrystallised from the mixture of ethanol and acetone (V∶V＝1∶1). The product and intermediates were characterized by IR, ¹H NMR, MS spectra and elemental analysis.

Key words: calix[4]resorcinarene, solvent-free synthesis, star compound, p-phenylene- dialdehyde, pentaerythritol