“Sexting” is generally defined as the exchange of sexual media content via the internet. However, research on this topic has underscored the need to seek greater consensus when considering different conceptual elements that make up this definition. The aim of this study was to develop and validate an instrument for measuring sexting among adolescents, in order to cover a gap identified in the previous literature. The Adolescent Sexting Scale (A-SextS for short) was developed for validation on a sample of 579 Spanish secondary school pupils between the ages of 11 and 18. Evidence for face, content, concurrent, and criterion validity were assessed. A comprehensive set of 64 items, covering six defining characteristics of sexting (e.g., actions, recipient, media format, degree of sexual explicitness), was constructed after conducting an extensive literature review, two discussion groups, and a pilot study. Sexting prevalence rates measured by A-SextS were mostly concurrent with those found in previous studies. A-SextS subscales produced statistically significant positive associations with pornography consumption and physical sexual intercourse. The study shows that A-SextS can be an integrating instrument that facilitates a rigorous and comprehensive assessment of adolescent sexting experiences, as well as the formulation of an operationalized definition of the practice of sexting.