The arrival of new media technologies has the potential to affect education radically. Understanding of the behavioral and intentional reactions of students toward such innovations has become a new issue for academics and educators. The present study develops a Chinese-version Media Literacy Self-assessment Scale (MLSS), including the subscales of media application skills, learning with media, and attitudes toward media, to assess media literacy in early adolescents. More than 1,500 fifth and sixth graders in Taiwan responded to the scale. The results reveal that the MLSS had adequate validity and reliability in assessing elementary school students’ perceptions of media literacy in digital learning environments. In addition, the findings of this study reveal the existence of gender differences on the subscales and the real affect of library instruction and Internet experience on the media literacy of students. Finally, it advances suggestions for future research.