The experience sampling method was transformed into a digital format and examined in the Web environment to elicit on-line Web users’ experiences through multiple iterations of an on-line questionnaire. By sampling Web users’ on-line experiences and detecting Web users’ situated experiences from a time point very close to their actual experiences, this tool can collect reliable and valid data with minimal distortion. This tool can effectively and unambiguously tap Web users’ internal experiences associated with their use of the Web. Data on Web users’ on-line experiences were collected and analyzed to evaluate the reliability and validity of the tool. This tool should be applicable to other fields to elicit Web users’ situational experiences and perceptions in a variety of research contexts.