Many text books and publications do not focus on the necessity of chain tilting in crystalline lamellae of oligomers and polymers, a fundamental aspect of their crystallization already discussed by Flory. Herein we investigate the chain tilt of ethylene oxide oligomers (EOs) containing various midchain defects by WAXS, SAXS and solid state 13C MAS NMR spectroscopy. At low temperatures, one out of the two EO chains of EO9-meta-EO9 and EO11-TR-EO11 containing a 1,3-disubstituted benzene or a 1,4-disubstituted 1,2,3-triazole defect in central position of the oligomer chain forms crystals and the other EO chain as well as the defect remain in the amorphous phase. The aromatic midchain defect of these two oligomers can be incorporated into the crystalline lamella upon heating below Tm. Then, the adjoining amorphous EO chain crosses from the lamellae to the amorphous regions at an angle ξ, which is preordained by the substitution pattern of the aromatic defect, revealing that the chain tilt angle ranges between 36° ≤ ϕ ≤ 60°.