Understanding crystallization behavior is integral to the design of pharmaceutical compounds for which the pharmacological properties depend on the crystal forms achieved. Very often, these crystals are based on hydrophobic molecules. One method for delivering crystal-forming hydrophobic drugs is by means of lipid nanoparticle carriers. However, so far, a characterization of the potential crystallization of fully hydrophobic molecules in a lipid environment has never been reported. In this work we investigate the crystallization behavior of two model hydrophobic chains, n-eicosane (C20) and n-triacontane (C30), in phospholipid bilayers. We combine static 2H nuclear magnetic resonance (NMR) spectroscopy and differential scanning calorimetry (DSC) and show that C30 molecules can indeed crystallize inside DMPC and POPC bilayers. The phase transition temperatures of C30 are slightly reduced inside DMPC, and rotator phase formation becomes a two-step process: Preorganized n-alkane chains assemble in rotator-phase crystallites just as fast as bulk C30, but further addition of molecules is notably slower. Under the same isothermal conditions, different crystal forms can be obtained by crystallization in the membrane and in bulk. In excess water conditions, homogeneous nucleation of C30 is observed. The initial anisotropic molecular arrangement of C30 molecules in the membrane is readily recovered upon reheating, showing reversibility. The shorter C20 molecules on the other hand become trapped in the DMPC membrane gel-phase upon cooling and do not crystallize. This work marks the first observation of the crystallization of hydrophobic chains inside a lipid bilayer environment. As such, it defines a fundamental starting point for studying the crystallization characteristics of various hydrophobic molecules in lipid membranes.