This paper describes the mechanisms of ion and electron transport in nanostructured insertion electrode materials such as metal oxide electrochromics and/or Li ion batteries. A general description is given of cases of insertion into a short path region predicted by the geometric disposition of insertion materials in nanostructural electrodes, designed mainly by connected spherical-like particles and nanofibers, both protruding from the cur-rent collector substrate. The short path scheme for ion diffusion (nanometer length) permits an ion storage mechanism to be treated as a capacitance charge rather than a diffusion process, an effect that is dubbed the "nanoscale effect". As a result of heterogeneous charge-transfer resistance, the intercalation sites may be seen as the occupation of an ion immobilized-like state. A scheme of an ion trapping-like state represents, in the present case, an ion-binding process occurring during the intercalation reaction, like Li+ forming a bond to a bridging-type oxygen in metal oxide based insertion materials. The model predicts a relaxation process for the intercalation reaction which is more clearly visible in cases of fast transport (occurring throughout the solid and liquid/electrolyte phases of a nanosized macrohomogeneous medium) and/or high state-of-charge. The characteristic frequency of this relaxation process can be used to predict the rate of Li ion intercalation reaction in different nanosized host materials.