Planar, terpyridine-based metal complexes with the Sierpiński triangular motif and alkylated corners undergo a second self-assembly event to give megastructural Sierpiński pyramids; assembly is driven by the facile lipophilic-lipophilic association of the alkyl moieties and complementary perfect fit of the triangular building blocks. Confirmation of the 3D, pyramidal structures was verified and supported by a combination of TEM, AFM, and multiscale simulation techniques.