Note: If you don't have access to perform these actions, please work with your Marketing Cloud Administrator to complete them.
If you receive an error saying "There was an error communicating with Salesforce, verify your connected app is set up properly and try again" after attempting to enter your Salesforce.com Username in Marketing Cloud, then your Salesforce user is likely not configured for authentication with Marketing Cloud Connect. Please ensure that the "Marketing Cloud for AppExchange User" checkbox and "Marketing Cloud for AppExchange Admin" (if you are an Admin) checkbox are selected on your Salesforce user profile. The "Marketing Cloud Connected App" permission set will also need to be assigned to your user as well. Please refer to the "Marketing Cloud Connect User Types and Permissions" documentation and the "Set Up Authentication" documentation below for more information.
Additional Salesforce Help Resources:
Marketing Cloud Connect User Types and Permissions
Set Up Authentication
Marketing Cloud Connect Connected App
Connect Marketing Cloud API User in Marketing Cloud Connect
Manage Users
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