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1. You probably knew that pressing the Tab key hides the toolbar and palettes, but you can also press Shift+Tab to hide only the palettes (thereby leaving the toolbar visible).
2. Snap your palettes to the nearest screen edge by Shift-clicking on their titlebars.
3. Minimize palettes by double-clicking on their (names in the) palette tabs. Use the minimize button on the palette titlebars to cycle between: compact mode (minimum number of options / contents visible) and contents mode (view all palette options / contents).
Note: (Photoshop 6) You can also double-click the toolbar's titlebar to minimize it.
4. Press Enter (or double-click on a tool icon in the toolbar) to reveal the Options palette for the currently active tool; alternatively, you may choose Window » Show Options from the menus to reveal the Options palette.
6. To change the (document size) information displayed in the status bar (bottom of the screen -Window » Show Status Bar), click on the > button and choose a new item from the pop-up menu. Click on the status bar (to the left of the > button) to display the Print Size of the current document. Alt-click to see the image dimensions and resolution. Ctrt-dick for Tile information.
7. You can fill the (gray) canvas borders with the foreground color by Shift-clicking on it with the Paint Bucket tool [K].
Note: To replace the default color, change the foreground color to 25% gray (R192,G192,B192) and Shift-click on the canvas border again.
8. Hold down the Alt key to change any Cancel button into a Reset button (in any dialog box); this allows you to easily restore values without having to Cancel and come back.
9. Use the Caps Lock key to turn Precise Cursors on / off.
Note: This does not work if Precise Cursors are already enabled in the Preferences [Ctrl+K, Ctrl+3] (File » Preferences » Display & Cursors...).
10. Press "F" to cycle between three different Full Screen modes (or use the Mode buttons near the bottom of the toolbar).
Tip: Press Shift+F to toggle the menus in Full Screen mode.
11. Double-clicking on Photoshop's background (the gray background) will summon the Open command [Ctrl+0] (File » Open...).
12. Shift-click on the color ramp (on the Color palette [F6] (Window » Show Color)) to change the spectrum. Alternatively, you may either right-click on the color ramp or open the Color palette menu to select an alternate color mode.
13. Right-click on an image window's titlebar to quickly access features like Canvas Size, Image Size and Duplicate.
14. Pausing the mouse pointer over an image window's titlebar will reveal (via a tool tip) the full path of the current document.
15. Add a custom color to the Swatches palette (Window » Show Swatches) by clicking on any empty (gray) area. Remove a color by Ctrl-clicking on it. Replace a color by Shift-clicking on it. Insert a new swatch color (between two other colors) by Alt+Shift-dicking on either color.
16. Use the Hexadecimal Color Field (#) in the Color Picker to copy and paste color values from one place in Photoshop to another (or even to another application that supports Hexadecimal color values).
17. To increase / decrease the size of the Curves window [Ctrl+M] (Image » Adjust» Curves...), click on the maximize / minimize button.
Note: Clicking the maximize / minimize button toggles the Curves grid between 171 pixels and 256 pixels wide. For greater accuracy, use the larger grid, since you have control over all 256 shades of gray in the image (compared to 171 shades by using the small grid).
18. (Photoshop 6 and ImageReady) Alt-click on a triangle icon to expand or collapse all child elements of an action, action step, layer style, or layer set.