Formyl groups were introduced to the para positions of the three easily accessible calix[4]arene conformers immobilized by four propyl or isopropyl groups by Duff reaction. Propyl group led to exhaustively formylated products due to the weak steric hinderance effect. While as for the isopropoxy calix[4]arenes, with the increase of steric hinderance, 1,3-alternate conformer gave exhaustively formylated product with no alkyl group dealkylating; partial cone conformer gave the tetraformylated proximal A,B-diether in 1,3-alternate conformation; and cone conformer led to triformylated derivatives accompanied by the selective dealkylations of three or two diametrical alkyl groups. The results indicated that the structures of the products were greatly influenced by the steric hinderance effect of the starting compounds.