In recent years there has been widespread interest in the implementation of information and communication technologies (ICT) in schools. While most studies primarily focus on the use of ICT in teaching and learning, little attention has been given to their incorporation as a professional tool outside the classroom. Using a digital inequality approach, the aim of this paper is to develop and test a model of the factors that affect teachers’ professional use of ICT, particularly the Internet, in primary and secondary schools. One thousand four hundred and five (1,405) teachers from a representative sample of 536 primary and 273 secondary schools in Spain were surveyed. The dependent variables include attitudes towards the professional use of ICT and the use of the Internet in professional practice. The explanatory variables are the socio-demographics, school-level information, frequency of Internet access within and outside the school, educational ICT training, digital literacy, and organisational development. Controlling for socio-demographics and school-level information, multiple regression analyses are used to make inferential judgments and test the separate effects of the independent variables. Findings suggest that technological factors and organisational practices are important predictors of ICT appropriation for professional purposes.