Two conformational isomers of p-tert-butylcalix[4]arene hexanoate were prepared from the reaction of-p-tert-butylcalix[4]arene and hexanoly chloride in the presence of AlCl3 in CH2Cl2 and their structures were determined by NMR spectra and X-ray diffraction as a cone and a 1,3-alternate conformer, respectively. The crystal of cone conformer (C68H96O8·(CH3)2CO) is triclinic, P, a=15.066(1) , b=16.063(1) , c=16.365(1) , α=79.75(2)o, β=109.95(2)o, γ=80.32(0)o, V=3602.7(4) 3, Z=2. The intensity data were collected on Simens SMART diffractometer/CCD area detector. The structure was solved by direct method and refined by least-squares calculations to a final R value of 0.144 for 4638 observed reflections. The molecular conformation is distorted symmetric cone with the flattening A and D phenyl rings. The crystal of 1,3-alternate conformer (C68H96O8·2CHCl3) is orthorhombic, Pca21, a=34.586(5) , b=10.207(3) , c=20.394(4) , V=7199(3) 3, Z=4. The intensity data were collected on an Enraf-Noninus CAD-4 Diffractometer with a graphite monochromated Mo-K radiation. The structure was solved by direct method and refined by least-squares calculations to a final R value of 0.152 for 2241 observed reflections. The molecule has a pseudo mirror symmetric 1,3-alternate conformation.