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Creating a unique External ID field on Accounts in Salesforce for matching is an effective way to prevent duplicates when importing Accounts from an external system. This method ensures that each record has a distinct identifier that can be easily referenced during the import process. By leveraging an External ID, the system can match incoming records with existing ones in Salesforce based on this unique value, allowing for a seamless import without the risk of duplicating data.

When importing data, if the External ID already exists in Salesforce, the import process can update the existing record instead of creating a new one. This functionality is crucial for maintaining clean and organized data, especially in scenarios where multiple parties might be importing data or when syncing large datasets from external systems.

Other methods such as creating a formula field to identify matches or using VLOOKUP could be more complicated and less efficient in preventing duplicates during the immediate import process. Additionally, substituting the Salesforce ID with an external system’s ID does not provide a reliable mechanism for matching existing records, especially if there’s no guarantee that the external system IDs will be unique or correlate with Salesforce records effectively.