Nanopores with symmetry-breaking features possess unique ion transport properties that are inaccessible in bulk or amorphous systems, offering new avenues to develop or improve functions in energy conversion, logic operations, neuromorphic computing, synapses, separation, chemical sensing, and iontronics. Solid-state nanopores (or nanoporous membranes) are versatile platforms for fundamental studies such as structure-property correlations considering the easy fabrication and rich ion transport dynamics revealed in previous research. In this work, I present a strategy for controlling the rectification and transport hysteresis through regulation of space charge generated by the redox chemistry in single conical nanopipettes and ensemble nanopores in anodic aluminum oxide membrane (AAO). Symmetry-breaking properties are either barrier oxide layer (BOL) of AAO or controlled assembly of Redox polymer poly(3,4-ethylene-dioxythiophene): poly(styrene sulfonate) (PEDOT:PSS) into the two types of nanofluidic devices. Oxidation and reduction of the PEDOT or changes in the oxygen/aluminum vacancy in BOL of AAO change the distribution of space charges and the availability of mobile ionic charge carriers, thereby change the ionic conductivity, notably rectification, hysteresis, negative differential resistance, and switching in conductivity states. Electrochemical properties were studied using cyclic voltammetry, chronoamperometry, and impedance spectroscopy. The results from those different techniques reveal characteristic features for short- and long-term memory as well as promising ion selectivity and iontronics functions. Interpretation of those fundamental experimental transport studies is further supported by finite element simulation.