The correct way to use a custom account field in Salesforce for segmentation in Marketing Cloud Account Engagement is to create a custom account field in Marketing Cloud Account Engagement and map it to the account field in Salesforce. This will allow you to sync the data between the two systems and use the custom field as a segmentation criterion in Marketing Cloud Account Engagement. You can create a custom account field in Marketing Cloud Account Engagement by going to Settings > Object and Field Configuration > Prospect Account Fields > Add Custom Field. Then, you can map it to the corresponding account field in Salesforce by selecting it from the drop-down menu
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