The N‐tetrachlorophthaloyl‐(TCP‐)amino protecting group has been evaluated for use in solid‐phase peptide synthesis. The TCP group was unaffected by exposure to either piperidine or N,N‐diisopropylethylamine (DIEA), which suggests compatibility with both Fmoc and Boc solid‐phase synthesis protocols. Quantitative TCP removal was achieved by treatment with hydrazine/DMF (3:17) at 35 °C for 30 min or with ethylenediamine/DMF (1:200) at 50 °C for 30 min. Several C‐terminal peptide amides were synthesized successfully by following protocols that use hydrazine/DMF (3:17) at 40 °C for 1 h for repetitive deprotection. Treatment of TCP‐amines with methylamine or with diamines did not give the corresponding amines (deprotected), but rather the appropriate N,N′‐disubstituted tetrachlorophthalamides, which corresponds to a single ring‐opening step. This observation was harnessed to prepare linear and macrocyclic peptide−arene hybrids based on the mild reaction of the parent TCP compound with 1,3‐diaminopropane/DMF (1:49) at 25 °C for 5 min. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)