The aim of our study is to improve the understanding of the different behavioral intentions of referees and assistant referees in different FIFA (International Federation of Association Football) confederations towards Multimedia Teaching Materials as learning tools. To achieve this goal, we carry out a survey of 214 elite referees and assistant referees and we propose a research model with the variables perceived usefulness, perceived ease of use, perceived enjoyment, perceived self-efficacy, multimedia instruction, previous experience with technology and self-paced learning. These variables were taken from previous educational technology research. Among these models we mainly take into account the Technology Acceptance Model, the Motivational Model and the Social Cognitive Theory. To assess the relationships between the constructs, we develop an analysis based on a Structural Equation Modeling (SEM), specifically Partial Least Squares (PLS). The results of this study confirm that referees and assistant referees are willing to use Multimedia Teaching Materials to assist them in their learning activities as long as they perceive the materials to be useful, enjoyable and easy to use and whenever the course contents are multimedia.