At sunrise or sunset, the sky turns red, orange or yellow because sunlight is traveling through more air when the sun is low in the sky. The long path through the air means most of the blue and other colors with shorter wavelengths have been scattered out in different directions. Few reach your eye. You see the yellow, orange, and red colors which pass more freely through the air. The most vivid sunrises and sunsets, however, are brought by volcanoes and forest fires. This is because the expelled particles are just the right size to scatter light in the red end of spectrum.
Source: http://www.wrh.noaa.gov/otx/outreach/ttalk/colors.php
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