Understanding the Duotone Color Mode
The duotone color mode, converts a grayscale image into duotone (2-color), tritone (3-color), and quadtone (4-color) image using 2 to 4 custom inks. Duotones are frequently used to increase the tonal depth of a grayscale image. For example, most printing presses produce 50 levels of gray per color. By converting an image into a duotone, and using black and a mid gray, the press can produce a grayscale image with more dynamic range. A more common method for employing the duotone color mode is to create an image with an overall colorcast. For example, converting the grays in the image to sepia tone. If you're uncertain how to create the proper color mix for a duotone image, Photoshop comes equipped with dozens of sample duotone color values.

Convert an Image to Duotone
Open an image.
Click the Image menu, point to Mode , and then click Duotone .IMPORTANT
Before converting an image into a duotone, it must first be in the grayscale color mode.Click the Type list arrow, and then select from the following options:
Monotone.
Uses one color to generate image tone (limited dynamic range).
Duotone.
Uses two colors to generate image tone (better dynamic range for B&W images).
Tritone.
Uses three colors to generate image tone (great dynamic range, with a variety of color combinations).
Quadtone.
Uses four colors to generate image tone (best dynamic range, practically unlimited color choices).
Click the Overprint Colors button to adjust how the colors will display when the inks are printed.
Click OK .