Why it happens
Vinaigrette is an emulsion of oil and vinegar, which naturally don't mix. Shaking or whisking breaks the oil into tiny droplets spread through the vinegar, but without anything to hold them apart they soon join up again and the oil floats to the top. This is called a temporary emulsion. Ingredients such as mustard, honey and egg yolk act as emulsifiers, helping the droplets stay suspended for longer.