User experience (UX) is defined as “a person’s perceptions and responses that result from the use or anticipated use of a product, system, or service” (ISO 9241-210). This definition is directly related to the inner states of the experiencer in terms of both cognitive and affective dimensions. On the other hand, it covers the perception, evaluation and decision related to the product in use. It has been important to understand this integrated experience by examining different research methods and comparing these findings. The conventional methods including the surveys/questionnaires, think-aloud procedures and in-depth interviews have contributed considerably for understanding the problems during the use of internet sites for shopping. On the other hand, the use of neuroscientific and psychophysics methods, also mentioned as neuroscientific and biometrics in this text, has also grasped attention with the exciting idea of providing objective means of understanding cognitive and affective processes during the user experience under online environments (Chai et al., 2014). Despite the fact this idea has also strong limitations such that an attached device is usually necessary, it has been of interest for many researchers to explore such potential use in this interdisciplinary area of research. This empirical and exploratory study has aimed to understand the user experience of first-time buyers during e-shopping and specifically during product search in e-commerce via the use of neurophysiological and psychophysics research methods as well as the conventional methods. The main research scope is about understanding the potential negative factors, specifically obstacles, during e-shopping processes by both neurophysiological and conventional methods. We have also aimed to compare and to contrast the consistencies and differences between the findings of conventional and neurophysiological-biometric methods.