Organic bioelectronics develops electronic devices at the interface with living systems using organic electronic materials. These devices can identify various chemical species and regulate the operation of individual cells, tissues, or organs. A famous organic bioelectronic device is the organic electrochemical transistor (OECT), a highly versatile circuit component that has been used in applications spanning from biosensing to neuromorphic computing. OECTs can be operated in aqueous electrolytes and use organic mixed ionic-electronic conductors (OMIECs) in their channel (and sometimes as gate electrode coating) that can transport electronic and ionic charges, making them ideal for bridging biological systems and silicon-based electronic devices. Electron-transporting (n-type) OMIEC materials have received particular attention because high-performance n-type OECTs can be used to build inverters, sensors, and complementary amplifiers. However, electron transport in an aqueous and ambient environment under the application of electrical fields is a complex phenomenon that requires in situ investigation techniques. Understanding how films operate in such media can allow to construct novel sensors and eliminate the loss processes. This Ph.D. dissertation focuses on the impact of the environment, specifically oxygen, and light, on the performance of n-type OECTs and shows how to use this knowledge to develop OECT-based glucose sensors and photodetectors. Chapter 1 introduces the mixed charge transport phenomenon in conjugated polymers and how to use it in OECT operation. OECT fabrication and various designs are described, setting the ground for the sensors we will show in the following chapters. The experimental procedures used to evaluate the critical figures of merit of the materials and the transistor performance are described in detail. Chapter 2 introduces how OECTs can be used to transduce biochemical binding events. When employing the OECT platform for biochemical sensing, it is essential to differentiate between the faradaic, capacitive, and potentiometric contributions to the sensor response. Understanding the underlying mechanisms is critical for optimizing performance. This chapter explains these different sensing mechanisms with literature examples. Chapter 3 compiles all experimental details relevant to the investigations presented in Chapters 4 and 5. Chapter 4 investigates the working mechanism of a novel n-type OECT-based glucose sensor relying on an enzymatic reaction. This chapter shows the oxygen reaction reactions and the importance of monitoring contact potentials during device operation to understand how detection occurs. The work unveils the role of the oxygen sensitivity of the n-type material on the sensor operation and suggests paths to improve performance. Chapter 5 explores the interactions of light with n-type OMIECs and how to utilize them to build water-compatible phototransistors. The first part of the chapter involves a characterization of the light/matter interplay of an n-type film and a demonstration of how to use it to build a photoelectrochemical transistor. The second part of the chapter expands this work to other n-type materials and assesses their light sensitivity, building a relationship between material property and device performance. Since most detection events lead to a change in the surface of materials, techniques that monitor surface roughness and profile changes in situ can be useful. Chapter 6 describes an atomic force microscopy (AFM) setup that can be used to investigate binding events and electrochemical doping and de-doping dynamics of OMIEC films. This chapter is intended to assist researchers in developing in-operando AFM procedures studying OMIEC films.