Ionic self-assembled multilayer (ISAM) thin film nanostructures, including highly porous and conductive gold nanoparticles (GNP), and highly porous and thermally stable silica nanoparticles (SNP), were fabricated via the layer-by-layer (LbL) self-assembly technique. Their application in ionic polymer-metal composite (IPMC) electromechanical bending actuators and microfabricated gas chromatography (microGC) devices were investigated and significant performance improvements of these devices were achieved. IPMC bending actuators, consisting of an ionic electroactive polymer (iEAP) membrane as backbone, ionic liquids (IL) as electrolyte, and ISAM GNP thin film as porous electrode, were fabricated and investigated. The influences of humidity, conductive network composite (CNC), and IL uptake on the bending performance were examined and discussed. An equivalent circuit model to simulate both the electrical and mechanical responses was also proposed and experimentally verified. Moreover, IPMC actuators made from other newly synthesized iEAP membranes were fabricated and tested. Some of them showed promising performance that was comparable or even better as compared to the ones made from Nafion. LbL fabricated ISAM SNPs thin film coatings were also applied in the microGC devices including micro fabricated thermal preconcentrators (microTPC) and separation columns (microSC) as adsorbent and stationary phase materials, respectively. New fabrication approaches were developed to selectively coat uniform conformal ISAM SNP coatings in these devices with different 3D microstructures. Thus, functionalized microTPCs and microSCs showed good performance, which can be further improved by using the ISAM SNPs coating as a nanotemplate for modifying additional polymer adsorbents or as the anchor sites for incorporating functional molecules for targeting detection. / Ph. D.