Macao participated in OECD’s PISA 2006 Scientific Literacy Study. A representative sample of 4,760 students was tested on scientific literacy performance. Students’ responses to the ICT Familiarity Questionnaire allow the researchers to assess the relationship of ICT usage (e.g. browse the Internet for information) and ICT self-efficacy (e.g. create multi-media presentations) with scientific literacy performance. Through latent profile analyses (LPA) of the ICT usage and ICT self-efficacy variables, a typology of ICT familiarity of 3 latent classes of students is validated, and patterns of ICT usage and ICT self-efficacy of the three latent classes are found to be associated with distinctive levels of scientific literacy performance. Using a person-centered data-analytical approach, it is possible for schools to design intervention studies tailored to the defining characteristics of the typology of ICT users. This study is important for countries to chart trends of ICT usage in the three-yearly PISA assessment.