It’s very common practice the administrators to get notification mail when a new order is placed on the shop. Here is how to activate this feature in Magento for free (there is paid Admin Notification Module as well):
Log in into admin area, then go to System->Configuration menu. Scroll down to Sales section and click on the Sales Emails and select the first section Orders. Enter your admin e-mail in the field “Send Order Email Copy To”.
And here comes the tricky one 🙂 Select the option “Separate email” from the “Send Order Email Copy Method” field. I don’t know why, but if it’s selected “Bcc”, the e-mail to the admin wasn’t send.
It’s possible that this is fixed in the versions above 1.2.x, but I haven’t tested.
hope this helps someone.