Alignment has taken on increased importance given the current high-stakes nature of assessment. To make well-informed decisions about student learning on the basis of test results, assessment items need to be well aligned with standards. Project 2061 of the American Association for the Advancement of Science (AAAS) has developed a procedure for analyzing the content and quality of assessment items. The authors of this study used this alignment procedure to closely examine 2 mathematics assessment items. Student work on these 2 items was analyzed to determine whether the conclusions reached through the use of the alignment procedure could be validated. It was found that the Project 2061 alignment procedure was effective in providing a tool for in-depth analysis of the mathematical content of the item and a set of standards and in identifying 1 particular content standard that was most closely aligned with the standard. Through analyzing student work samples and student interviews, it was also found that students' thinking may not correspond to the standard identified as best aligned with the learning goals of the item. This finding highlights the potential usefulness of analyzing student work to clarify any additional deficiencies of an assessment item not revealed by an alignment procedure.