Measuring the business-IT alignment (BITA) of an organization determines its alignment level, provides directions for further improvements, and consequently promotes the organizational performances. Due to the capabilities of enterprise architecture (EA) in interrelating different business/IT viewpoints and elements, the development of EA is superior to support BITA measurement. Extant BITA measurement literature is sparse when it concerns EA. The literature tends to explain how EA viewpoints or models correlate with BITA, without discussing where to collect and integrate EA data. To address this gap, this paper attempts to propose a specific BITA measurement process through associating a BITA maturity model with a famous EA framework: DoD Architectural Framework 2.0 (DoDAF2.0). The BITA metrics in the maturity model are connected to the meta-models and models of DoDAF2.0. An illustrative ArchiSurance case is conducted to explain the measurement process. Systematically, this paper explores the process of BITA measurement from the viewpoint of EA, which helps to collect the measurement data in an organized way and analyzes the BITA level in the phase of architecture development.