Polymers that dissolve and conduct lithium ions are of great interest in the application of rechargeable lithium batteries. It is generally believed that the transport of ions in these systems is facilitated by rapid segmental motion typically found in rubbery, amorphous polymers. In this paper, we demonstrate that chemically identical ethyleneoxy-containing domains of a block copolymer exhibit comparable conductivities when in an amorphous or a crystalline state. An important feature of this study is the use of sequence-defined block copolypeptoids synthesized by submonomer solid-phase synthesis. Two structurally analogous ethyleneoxy-containing diblock copolypeptoids poly-N-(2-ethyl)hexylglycine-block-poly-N-2-(2-(2-methoxyethoxy)ethoxy)ethylglycine (pNeh-b-pNte) and poly-N-decylglycine-block-poly-N-2-(2-(2-methoxyethoxy)ethoxy)ethylglycine (pNdc-b-pNte) with 18 monomer units per block were synthesized. Both diblock copolypeptoids have the same conducting block, pNte, but different nonconducting blocks: pNeh, which is amorphous, and pNdc, which is crystalline. Both diblock copolypeptoids self-assemble into a lamellar morphology; however, pNte chains are amorphous in pNeh-b-pNte and crystalline in pNdc-b-pNte. This provides the platform for comparing lithium ion transport in amorphous and crystalline polymer domains that are otherwise similar.