Polymer electrolytes continue to offer the opportunity for safer, high-performing next-generation battery technology. The benefits of a polymeric electrolyte system lie in its ease of processing and flexibility, while ion transport and mechanical strength have been highlighted for improvement. This report discusses how factors, specifically the chemistry and structure of the polymers, have driven the progression of these materials from the early days of PEO. The introduction of ionic polymers has led to advances in ionic conductivity while the use of block copolymers has also increased the mechanical properties and provided more flexibility in solid polymer electrolyte development. The combination of these two, ionic block copolymer materials, are still in their early stages but offer exciting possibilities for the future of this field.