This paper shows that 25‐propyloxy‐26,27‐dibenzoyloxy‐calix[4]arene can be a convenient precursor for the formation of inherently chiral configuration on the calixarene platform. The methods for sequential regioselective debenzoylation and electrophilic substitution on the upper rim were developed. The inherently chiral calix[4]renes with two and three different functional groups on the upper rim were synthesized.