Hi Priya,
I think this is possible via the web portal or the Azure DevOps CLI command, you can get a list of the users in your organization and view their access level information, you must be the Organization owner or a member of the Project Collection Administrators group.
If the script is required please follow this guide and it lists a script for exporting the users and information.
how-to-list-all-users-and-group-permissions-on-azure-devops-using-azure-devops-cli-54f73a20a4c7
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