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Industry 4.0 (I4.0) has become a widely accepted manufacturing paradigm across a wide range of industries. It includes an array of various approaches, tools, techniques, and methods. They were known to researchers before, but when combined they build a new reality, which needs procedures for the assessment of technologies and manufacturing processes. Current assessment methods often fail to incorporate economic, environmental, and social impacts simultaneously in an integrated way. The potential implementation of a sustainability assessment procedure on a larger scale is seen for (well-developed) Radio Frequency Identification (RFID) technology. The measures for assessment were identified through a literature review and validated by expert panels. Validation measures were quantified using multi-criteria decision making (AHP). Criteria ranking was used for reasoning if the assumed modular structure responded to the experts’ needs. To connect the existing research gap, a holistic and integrated assessment method for I4.0 applications, depicted in a structured way and tailored for RFID technology, is developed, which constitutes a research gap in current literature on this topic. Results showed that a modularized structure of approach (module—group of measures—measures [as indicators]) for RFID sustainability assessment, which depends on the complexity of this technology, may be a convenient method for assessment of I4.0 technologies. It was confirmed that all sustainability perspectives are important due to their contributions to supporting decisions and should be considered in the assessment of RFID. On the other hand, it can help managers and practitioners implement the assessment method in their practice to reduce pollution and save the environment.