The aim of this study was to develop a scale for assessing and predicting adolescents’ physical activity behavior in Spain and Luxembourg using the Theory of Planned Behavior as a framework. The sample was comprised of 613 Spanish (boys = 309, girls = 304; M age =15.28, SD =1.127) and 752 Luxembourgish adolescents (boys = 343, girls = 409; M age = 14.92, SD = 1.198), selected from students of two secondary schools in both countries, with a similar socio-economic status. The initial 43-items were all scored on a 4-point response format using the structured alternative format and translated into Spanish, French and German. In order to ensure the accuracy of the translation, standardized parallel back-translation techniques were employed. Following two pilot tests and subsequent revisions, a second order exploratory factor analysis with oblimin direct rotation was used for factor extraction. Internal consistency and test-retest reliabilities were also tested. The 4-week test-retest correlations confirmed the items’ time stability. The same five factors were obtained, explaining 63.76% and 63.64% of the total variance in both samples. Internal consistency for the five factors ranged from α = 0.759 to α = 0. 949 in the Spanish sample and from α = 0.735 to α = 0.952 in the Luxembourgish sample. For both samples, inter-factor correlations were all reported significant and positive, except for Factor 5 where they were significant but negative. The high internal consistency of the subscales, the reported item test-retest reliabilities and the identical factor structure confirm the adequacy of the elaborated questionnaire for assessing the TPB-based constructs when used with a population of adolescents in Spain and Luxembourg. The results give some indication that they may have value in measuring the hypothesized TPB constructs for PA behavior in a cross-cultural context.