Different architectures of Poly(ethylene glycol) (PEG) were synthesized via (CuAAC) click reaction and investigated for their crystallization behavior. In the first part, cross-linked PEG networks were synthesized which exhibit a random arrangement and broader size distribution of PEG crystallites in the network. Both melting temperature and degree of crystallinity was reduced after cross-linking. Swelling and solid-state NMR studies revealed an inhomogeneous network structure due to network defects. In the second part, one 1,4 disubstituted 1,2,3 triazole (TR) containing point defects was introduced in the middle of PEO chain. Temperature-dependent SAXS, WAXS, and solid-state NMR measurements reveal the incorporation of TR defect in the PEG crystal upon heating. In the last part, PEG samples having two TR rings, separated by n-alkyl spacers (n = 2-8) of different lengths were synthesized. An odd-even effect in the melting temperatures was observed. Temperature-dependent WAXS and solid-state NMR measurements reveal the complete incorporation of smaller-sized defects while partial incorporation of larger-sized defects in PEG crystals.