A series of complementary adenine and thymine alkyl derivatives were synthesized and characterized. Due to their amphiphilic-like chemical structure, these compounds, either in a pure state or in binary mixtures, form well developed lamellar structures from room temperature up to the clearing point. Hydrogen bonding between the recognizable moieties are responsible for the increased stability of the crystalline forms. The absence of stable liquid crystalline phases may also be attributed to the unfavorable shape of the alkylated nucleobases and of their complexes.