Email black and white list is an effective filter for outgoing(SMTP) and incoming(POP3) emails. You can either use the black list or the white list. Only email accounts in the white list are allowed when white list is enabled. Enable black list means allow all except those listed in the black list.
You can not block web-based email here. If you want to block web-based email, you need to configure the website black/white list. Please refer to "Website Black/white List Configuration".
Please note that the email black/white list is applied to the email user accounts which may be different with the email addresses.
Take Outlook as an example, click "Tools" -> "Accounts" -> "Mail" -> select your email -> "Properties" -> "Servers". As in Figure 1, the account is IMFirewall which will be scanned by the Black/white list.

To make blocking work, you can change an existing blocking level or add a new one. Here we start this example from adding a new blocking level.
As in Figure 2, add an new blocking level named "Blocking email".

As in Figure 3, you should check the "Customize email access rules".

For example, choose the "use black list". Add email accounts which you want to block to the "Black List". One account per line.
As in Figure 4, we add "abc@163.com" and "efg@163.com" to the "Black List" in order to block this two accounts.

Click "Modify" to save configurations.
You need to set the blocking level for computers which you want to implement this blocking policy. As in Figure 5, choose the "Blocking email" blocking level in the "Blocking rules". Remember to click "Save" to save configurations.
