Persistent pain following treatment for breast cancer (PPBCT) is a prevalent and complex clinical issue. Education together with physiotherapy have been shown to lessen pain and disability in chronic pain. Although the evaluation of the patient’s competences is a major part of the educational program, the published educational programs rarely describe the tools used to assess competences, especially regarding those related to decision-making and problem-solving. The aim of this study was to provide two competences assessment tools: the cross-cultural adaptation and validation of the Spanish version of the Revised Neurophysiology of Pain Questionnaire (R-NPQ) and practical cases of women with PPBCT. The Spanish cross-cultural adaptation was conducted following recognized criteria. Measurement properties testing included an analysis of construct validity (known-groups approach), reliability (internal consistency and test-retest reliability), responsiveness, interpretability, and feasibility. To promote a tool that would allow evaluation of the educational program competences, a group of experts developed three cases extracted from real contexts by means of an iterative process. A total of 80 women with PPBCT (mean age 56 years) and 81 physiotherapy students (mean age 20 years) participated in the measurement properties analysis. The three developed cases were presented to the same 80 women with PPBCT before and after the educational program. As we expected, students showed a significantly higher score (p < 0.001) than did women with PPBCT in the R-NPQ questionnaire, with a large effect size (d = 2.49), demonstrating good construct validity. The Cronbach alpha was 0.90 (95% CI, 0.87–0.92) and the intraclass correlation coefficient was 0.82 (95% CI, 0.73–0.88). A large effect size (5.2) was found, as we expected, between baseline and post-treatment scores, suggesting adequate responsiveness. In addition, identifying and analyzing, decision making, communicating needs, knowing how to manage, and problem-solving skills were evaluated through the three practical cases. Most women (88.75%) reached the highest level in the assessment rubric of the proposed practical cases. The Spanish R-NPQ is a comprehensible, valid, reliable, and responsive tool for Spanish women with PPBCT. The practical cases are a useful competence assessment tool and were well accepted by women with PPBCT. Further studies are needed to investigate more competence assessment tools and to investigate whether the achievement of different levels of competences has an effect on health behaviors.