Stefaans - This is all depending on how your provider / host is set up, but here's what I know about the two sending methods. PHP is often faster because it's simply generating a bunch of emails and doing one of two things with them:
A) Sending them all directly to the recipients email server, which is hard to program and I don't believe how ListMailPro handles it, or
2) Handing them all over to the SMTP server on your end, but all at once or in groups of preset amounts
The problem is, depending on how your provider treats large amounts of email, it's queue rules, etc. it is a considerably safer idea to use SMTP. With SMTP, you're establishing a connection and handing off the emails INDIVIDUALLY. Yes, you can set ListMail to hand it off slower, in groups, then pause, another group, pause, but it's still technically saying to the SMTP server (mind you, very quickly), here's an email, here's an email, etc. The point is, if SMTP can't deliver one instantly, it moves it to the back of the line and continues, but still only has to technically handle one at a time. With PHP, it's true that assuming the SMTP server can keep up, it'll get done much faster, but if it lags, you may actually lose a bunch of emails or they get pushed off for 8, 12, 24 hours if the queue is filled up with other people's mail. Again, it all depends on the settings your provider uses, but yes, PHP will appear faster, but is not what I'd recommend.