Well-ordered arrays of chiral molecular cavities have been constructed by self-assembly of inherently chiral calixcrown on Au(111) in 0.1 M HClO4 solution and investigated by scanning tunneling microscopy (STM). The chiral features are clearly observed in high resolution STM images. It is found that the adsorption of the two enantiomers results in the same ordered structures with upright orientation on Au(111). Moreover, only phase separation has been observed for the racemic mixture of the two enantiomers in the experiment. This is mainly due to the weak molecule-substrate interaction as well as asymmetric geometrical structures of the two enantiomers. The present study provides a simple method for construction of ordered arrays of chiral molecular cavities, which are of potential in chemical sensors, chiral recognition, and nonlinear optics.