An efficient solvent-​free procedure for the synthesis of pillar[6]arenes has been developed. The procedure involves the solid-​state condensation of finely milled 1,​4-​dialkoxybenzene and paraformaldehyde by grinding in the presence of a catalytic amt. of H2SO4. The use of org. solvents for the extn. of products has also been avoided. Operational simplicity, compatibility with various 1,​4-​dialkoxybenzenes, non-​chromatog. purifn. technique, high yields and mild reaction conditions are the notable advantages of this procedure. A large scale reaction demonstrated the practical applicability of this methodol.