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Utilizing CloudFormation StackSets for deployment is an effective method for implementing an AWS Config rule across multiple accounts because StackSets allow you to deploy CloudFormation templates to multiple AWS accounts and regions in a single operation. This feature is particularly beneficial in managing and enforcing consistent configurations across various environments, ensuring that the same rules are applied uniformly without the need for manual intervention in each account.

By employing StackSets, you can define your desired configuration through a CloudFormation template, which may contain the necessary definitions for your AWS Config rules. Once the StackSet is created, it provisions the configuration across all targeted accounts and regions, simplifying the management process and enhancing compliance and governance.

This approach automates the deployment process, reduces human error, and ensures that any updates to the rules can be efficiently propagated across all accounts. In contrast, manually deploying rules through the AWS Management Console may lead to inconsistencies and requires ongoing manual effort as accounts scale or change. Using on-premises management tools or creating a self-managed solution for configuration would introduce additional complexity and potential inefficiencies compared to the streamlined capabilities provided by StackSets in AWS CloudFormation.