Zinc oxide (ZnO) is a widely utilized, versatile material implemented in a diverse range of technological applications, particularly in optoelectronic devices, where its inherent transparency, tunable electronic properties, and accessible nanostructures can be combined to confer superior device properties. ZnO is a complex material with a rich and intricate defect chemistry, and its properties can be extremely sensitive to processing methods and conditions; consequently, surface modification of ZnO using both inorganic and organic species has been explored to control and regulate its surface properties, particularly at heterointerfaces in electronic devices. Here, the properties of ZnO are described in detail, particularly its surface chemistry, along with the role of defects in governing its electronic properties, and methods employed to modulate the behavior of as-grown ZnO. An outline is also given on how the native and modified oxide interact with molecular materials. To illustrate the diverse range of surface modification methods and their subsequent influence on electronic properties, a comprehensive review of the modification of ZnO surfaces at molecular interfaces in hybrid photovoltaic (hPV) and organic photovoltaic (OPV) devices is presented. This is a case study rather than a progress report, aiming to highlight the progress made toward controlling and altering the surface properties of ZnO, and to bring attention to the ways in which this may be achieved by using various interfacial modifiers (IMs).