Electron transporting (n-type) polymeric mixed conductors are an exciting class of materials for devices with aqueous electrolyte interfaces, such as bioelectronic sensors, actuators, and soft charge storage systems. However, their charge transport performance falls short of their p-type counterparts, primarily due to electrochemical side reactions such as the oxygen reduction reaction (ORR). To mitigate ORR, a common strategy in n-type organic semiconductor design focuses on lowering the lowest unoccupied molecular orbital (LUMO) level. Despite empirical observations suggesting a correlation between deep LUMO levels, low ORR, and enhanced electrochemical cycling stability in water, this relationship lacks robust evidence. In this work, we delve into the electrochemical reactions of n-type polymeric mixed conductors with varying LUMO levels and assess the impact of ORR on charge storage performance and organic electrochemical transistor (OECT) operation. Our results reveal a limited correlation between LUMO levels and ORR currents, as well as the electrochemical operational stability of the films. While ORR currents minimally contribute to OECT channel currents under fixed biasing conditions, n-type films self-discharge rapidly at floating potentials in a capacitor-like configuration. The density functional theory analysis, complemented by X-ray photoelectron spectroscopy, underscores the critical role of backbone chemistry in controlling O₂-related degradation pathways and device performance losses. These findings highlight the persistent challenge posed by ORR in n-type semiconductor design and advocate for shifting the focus toward exploring chemical moieties with limited O₂ interactions to enhance operational stability and performance at n-type film/water interfaces.