These materials encounter challenges such as low ionic conductivity at RT and high sensitivity to ambient conditions. The substantial anionic rotational disorder represents a formidable barrier to gaining structural insights during the high-conductivity phase. Elucidating the intricacies of structure-property relationships and comprehending the impact of anion exchange and substitution on ion transport mechanisms within cluster anion-type materials necessitates the application of sophisticated experimental and theoretical methodologies. Additionally, a notable deficiency exists in the establishment of systematic and universally applicable design principles for augmenting ionic conductivity. However, anion rotation is a key feature for designing high-conducting materials.