Nitration of thiacalix[4]arene, immobilized in the 1,3-alternate conformation, leads regioselectively to meta-substituted products. Depending on the reaction conditions, mono- and dinitro-derivatives can be isolated in acceptable yields. This unique substitution pattern is inaccessible in classical calixarene chemistry, and yields inherently chiral compounds, which makes thiacalixarenes very attractive as building blocks or molecular scaffolds.