Yes and no. When I connect the phone to the PC, I see two icons: Phone and Card:
If I click on the Phone icon, I can see folder for DCIM, Pictures, PhotoEditor, and others. I would expect to find the photos in the DCIM folder. But the DCIM folder is empty except for a sub-folder called Facebook which contains a few images I've saved from Facebook. No camera pics are present. I've gone into all the folders I can see, including Pictures and PhotoEditor. No pictures are visible.
If I click on the Card icon, I can see a DCIM folder as well. There's a Camera sub-folder there which contains pictures, but they're all old photos transferred from my old phone.
I can't find any pictures I've taken on the Galaxy S4 in any folders anywhere. For that matter, I've used ES File Explorer to browse the folders on the phone itself, and I can't find them using that method either.
The ONLY way I've been able to find the pictures is to use the Gallery app on the phone. All of the pictures show up. As I mentioned, the pictures are available and seem to be on the phone. I just can't locate any folder where they live!