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Step 5: Set the color of the highlights
Now that we have all our layers properly set up, we can specify the colors for the highlights and shadows of the image. First, start by double clicking on the Hue/Saturation icon of the Highlights layer in the layers palette. A Hue/Saturation window will appear where you can adjust the color. Checkmark Colorize near the bottom right of the Hue/Saturation window. Adjust the settings to achieve the color you want. Once you're done, the image should look tinted.
Step 6: Set the color of the shadows
Now we'll do the same thing to set the color of the the shadows. Edit the settings of the Shadows layer. You should see a live preview of the effect if you have the preview checkbox checked. The balance between the two colors may not be what you desire, but don't worry about that now because we'll work on it in the next step. For now, just get the color of the shadows to the color you like.
Step 7: Adjust the balance between the two colors
To adjust the balance, we'll be working on the layer mask of the highlights layer. Select the layer mask of the highlights layer then open the Levels tool (Ctrl+L or Image > Adjustments > Levels). Drag the middle input slider toward the left or right to alter the balance of the two colors. For example, in the image below, I gave the orange tint more strength so that the blue is only slightly visible.
Final Results
Original image
Split Toning Photoshop tutorial
You can also try out other color combinations instead of the traditional sepia/blue colors. Below are some examples of what can be done using this technique.
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