The Microsoft documentation How to Send Email Using SendGrid with Azure says that once an account has been set up you can see the SendGrid credentials by clicking on the key icon. This seems to have disappeared from the Azure portal. How can I find the SendGrid username for this service. I believe it is in the format of azure***@azure.com (see change username for ...?
I had a similar issue and took a guess to see if Azure CLI would give it to me and it does.
In the portal use the cloud shell option, this icon top right:
Change the shell type from PowerShell to Bash, if you have multiple accounts then you will need to select the right account
az account show
If not in the right account (UPDATE - if you have permissions to access all accounts then you won't need to switch accounts so you can skip to the final bit)
az account list
az account set -s <id of relevant subscription>
Then on the SendGrid resource blade go to Properties and copy the Resource ID and then run
az resource show --ids /subscriptions/xxxxxx/resourceGroups/xxxxx/providers/Sendgrid.Email/accounts/xxxxx
using your resource id obviously and in the output you will see the SendGrid username