The development of new chiral building blocks for constructing complex chiral architectures, such as macrocycles and cages, is both crucial and challenging. Although concave-shaped calixarenes have been established as versatile building blocks for the synthesis of cage compounds, there are no reports on cages constructed from chiral calix[4]arene derivatives. Herein, we present a straightforward and effective method for gram-scale synthesis of a new member of chiral calix[4]arene macrocycle enantiomers, namely, phenol[4]arene (PC[4]A). As a proof of concept, we functionalized these enantiomers into tetraformylphenol[4]arene (PC[4]ACHO) derivatives via the Duff reaction to construct chiral porous organic cages (CPOCs) using polyamine synthons. Specifically, we employ two fluorescent amine synthons, bis(4-aminophenyl)phenylamine and tris(4-aminophenyl)amine, to assemble with PC[4]ACHO enantiomers, resulting in [2 + 4] lantern-shaped and [6 + 8] truncated octahedral CPOCs, respectively. These structures have been unambiguously characterized by single-crystal X-ray diffraction and circular dichroism (CD) spectroscopy. Notably, the [6 + 8] truncated CPOCs exhibit internal diameters of approximately 3.1 nm, a cavity volume of around 5300 Å