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I want to have all files with an extension of .fw.png to open in Fireworks (not necessarily .png files though).

Is there a way to do this in Terminal?

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No. OS X file types ignore strings before the final .

You could rename all files x.fw.png to x.fw_png and then map that file type to FireWorks using many existing answers here but totally reprogramming how the OS parses for file extensions would be a hard nut to crack.

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If others search for how to change the default application for a normal extension like .png, you can use duti:

brew install duti;echo com.macromedia.fireworks .png all>~/.duti;/usr/local/bin/duti ~/.duti

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