p-tert- Butyltetramercaptotetrathiacalixarene 1 bearing 8 sulphur atoms was synthesised in high overall yield (80%). The synthetic strategy followed to prepare the compound 1 was based on the Newman and Kwart thermal rearrangement. The treatment of p-tert-butyltetrathiacalixarene 2 by N,N-dimethylthiacarbamoyl chloride under mild conditions afforded the tetra O-thiacarbamoyl derivative which under thermal transposition gave the S-thiacarbamoyl derivatives in quantitative yield. The treatment of the rearranged product by hydrazine hydrate gave the compound 1. The conformation adopted in the solid state by 1 was demonstrated by X-ray diffraction studies on a single crystal to be the 1,3-alternate. © 2003 Elsevier Ltd. All rights reserved.