I just called Apple to order a new laptop for my daughter and they discounted the price quite a bit (lower price than the normal employee or student discount). Had I walked into the store or ordered online, I don’t think I would have been offered this deal.
A couple of months ago, got a great deal on a new phone by calling Verizon (again prices that they did not offer either online or in the store).
So, when have you done well by calling to order stuff?
Yes, I’ve noticed that off and on. Right now, Verizon is coming to mind. I think it was a thread here that clued me to talk with a rep and get our way-too-expensive plan reduced. After I did that, I was so disgusted that they over charged me for years that I switched us to T-mobile.
Occasionally, I’ve gotten better hotel deals by calling instead of taking what’s offered on-line. I think this is generally offered when I have a rewards level that is above the basic level. I should probably call more often, it’s easier to do it all on-line.
I’m wondering if there’s any chance of doing this with an airlines - but if I’m not a high level frequent flyer on the carrier, I’m not about to sit on the phone for the hours it would probably take!
@kiddie, did you say or do anything specific to get the better deal?
I doubt it with airlines. I am Premier Platinum on United, had some regional premier upgrades that were expiring at the end of the month. I wanted to see if I could extend them and upgrade my son and his GF on a trip they are taking. I asked really, really nicely - but the answer was no 
Re Apple. I just bought an Apple computer (MacBook Pro) a few weeks ago. A friend of ours owns a small business and gets all his stuff from Apple. With his permission, I said that I was an employee of that company and they gave me a small discount. Only $140 on a $2000 computer but better than nothing.
I said make sure I get the education discount (which is typically $100) and he said I can give you a better discount than that (and I ended up with more like $200 off)
I have also called hotels and gotten better deals over the phone (I had forgotten that when I wrote my first post) - I have gotten college related hotels rates when I called (and there is nowhere to indicate those on the online reservation forms)
When I make the appts. To take my car in to get serviced I always ask the service advisor if he has any coupons for me. I almost always get at least 10% off.