By default when CentOS is installed not all the gnome utils are loaded in the system.
The screenshot utils is one of them that is not loaded.
So trying to take a screenshot would fail:
ERROR:
There was an error running gnome-screenshot: Failed to execute child process “gnome-screenshot”
Only the utilities below were available:
- gnome-about
- gnome-about-me
- gnome-appearance-properties
- gnome-at-properties
- gnome-at-visual
- gnome-audio-profiles-properties
- gnome-character-map
- gnome-control-center
- gnome-default-applications-properties
- gnome-desktop-item-edit
- gnome-display-properties
- gnome-font-viewer
- gnome-help
- gnome-keybinding-properties
- gnome-keyboard-properties
- gnome-keyring
- gnome-keyring-daemon
- gnome-mouse-properties
- gnome-network-properties
- gnome-open
- gnome-panel
- gnome-power-bugreport.sh
- gnome-power-manager
- gnome-power-preferences
- gnome-screensaver
- gnome-screensaver-command
- gnome-screensaver-preferences
- gnome-session
- gnome-session-properties
- gnome-session-save
- gnome-terminal
- gnome-text-editor
- gnome-thumbnail-font
- gnome-typing-monitor
- gnomevfs-cat
- gnomevfs-copy
- gnomevfs-df
- gnomevfs-info
- gnomevfs-ls
- gnomevfs-mkdir
- gnomevfs-monitor
- gnomevfs-mv
- gnomevfs-rm
- gnome-volume-control
- gnome-volume-control-applet
- gnome-wacom-properties
- gnome-window-properties
- gnome-wm
As you can see, gnome-screenshot wasn’t there.
To install the gnome-screenshot util:
sudo yum install gnome-utils
That should fix the problem and you should be able to take screenshots as you would normally expect:

The official webpage for the gnome-utils project