Four tetraethers (methyl, ethyl, allyl and benzyl) of p-tert-butyldihomooxacalix[4]arene were synthesized and their conformational behaviour studied by means of variable temperature 1 H NMR, including the determination of coalescence temperatures and ΔG ± . It was shown that the methyl ether still has some conformational mobility at -100 °C, the ethyl ether displays a fixed conformation at -20 °C and the other two derivatives are conformationally rigid at room temperature. The conformations obtained are the 1,2-alternate B and cone, depending on the derivative formed.