jats:titleAbstract</jats:title>jats:pHere we report the subcomponent self‐assembly of a truxene‐faced Znjats:sub4</jats:sub>Ljats:sub4</jats:sub> tetrahedron, which is capable of binding the smallest hydrocarbons in solution. By deliberately incorporating inward‐facing ethyl groups on the truxene faces, the resulting partially‐filled cage cavity was tailored to encapsulate methane, ethane, and ethene via van der Waals interactions at atmospheric pressure in acetonitrile, and also in the amorphous solid state. Interestingly, gas capture showed divergent selectivities in solution and the amorphous solid state. The selective binding may prove useful in designing new processes for the purification of methane and ethane as feedstocks for chemical synthesis.</jats:p>