Abstract Although tetrakis(2‐ tert ‐butyl‐4,5,6‐trimethylphenyl)distannene ( 9 ), the first tetraaryl‐distannene to be reported on, is stable in the solid state, only the monomeric stannylene 8 can be detected in solution. An X‐ray crystal structure analysis of 9 reveals a long tin‐tin bond length of 291.0(1) pm and a trans ‐bent Sn 2 C 4 framework with different fold angles of 21.4° and 64.4°.