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First, it looks to me as if the person used some stock photos and cut out the items she wanted/needed with the pen tool (found in the menu bar on the left about 2/3rds the way down).
Second, she then sized each pice to fit to scale. Edit>Transform> any combination of the options in that area.
Third, for the lips, it looks as if she painted them on using a combination of brushes with different colors and wet looks applied to the brushes.