Open Blender and start a new scene (CTRL+X to get rid of any older). You should get the default cube of any new Blender scene. Get into perspective view, from the camera (Num 0).

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With the cube being selected, enter in Edit mode (TAB Key) and activate the Face Select mode.

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Black dots appear in the center of each face. Click on the center of the face that is facing you in order to select it (Right Mouse Button).

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In the Editing menu (F9 key), press the New button in the Link and Materials tab.

Material should increase from 1 Mat: 1 to 2 Mat:2. Using the small arrows pointing toward the left or the right, on each side of this field, you can toggle from a material index to another. Come back to 2 Mat:2. By clicking on the Assign button, you will give at the selected face the material bearing the index 2 Mat: 2, while all the other faces will keep the 2 Mat: 1 index. Do it.

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In the Shading menu (F5 key), search in the Material tab the button which reads 2 Mat: 1. Change the Col of the Material in order to give it a green hue.

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Now click on the right arrow so that the button now reads 2 Mat: 2. Now, it is this second material index which is available for edition.

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Let's give to this index a new material by clicking on the lifts on the left of the MA:Material button and choose ADD NEW. The material now has become MA:Material.001. Change its color Col of the material.

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Leave the Edit mode (TAB key) and enter the shaded mode view (Z key). Here's our old mesh, with new colors!

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Article written on December the 21st, 2004.
Updated on November the 11th, 2008 for Blender 2.48a. Comments re-initialized