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I have to use an old version (2.45 - from 2007) of Blender*.

I'd like to change the material on one face only on an object. I understand that this can be done by clicking Assign on the Materials tab as described in this answer.

However, there is no Assign button in this version of Blender:

enter image description here

Can this still be done? Or is this a new feature introduced after 2.45?

*: The reason I have to use 2.45 is because I need a script written for this version. The script is VRM SVG exporter with some custom modifications. I'm exporting full-color SVG renders from all angles of an object. The built-in Freestyle SVG Exporter is not good enough for me.

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Yes, from the Editing Panel

In Blender 2.45 the button to assign a material to faces can't be found in the Shading Panel under the Material section like depicted in your image.

It is instead disjoined from the Material's editor (where you edit material's parameters) but linked to the the mesh itself, and so grouped with the sections that are about face's properties like shading, editing tools...

You can see the section in the lower left of the following image.

enter image description here

You can find more information in the official documentation.

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