When to use exposure compensation

exposure compensation is for when using semi auto modes (aperture & shutter), if you are using aperture priority and have set it to what you want in order to achieve the image you desire but the camera is still shooting to bright or dark, exposure comp will adjust that for you :D

If shooting manual, there's no point imho other than in some models it auto adjusts the exposure reading in the camera. I find my D700 likes a little + exposure comp no matter what mode I am using.
 
Aboout 90% of the aperture priority does a fine job if you tweak the results with some EC. You should quickly learn to predict when some EC will imporve the exposure for a particular scene. A typical scenario if a dark foreground object and a bright background, to get the subject well exposed you can pre-dial in some positive EC, alternatively you have some dark foreground which you want to be a silhouette while you appropriately expose the background then some negative works. In environments like snow then photos will be consistently underexposed (the meter will try to make everything 18% grey). Dial in some+ EC and you are good to go.


Some lenses and cameras also have consistent exposure errors, so correcting this can be helpful to reduce PP time.

Alternatively, you should always expose to the right as far as possible (ETTR). If you are not checking the histograms after each photo but a being lazy then if you already dial in 0.7-1.3 stops of EC then you can consistently expose to the right and just check for highlight clipping. If you bring everything back in post then you can pull far more shadow detail
 
I always dial in at least 1/3 to 2/3 generally.

When in a mostly white scene i dial in more.

When shooting into a light source i dial in even more.

This is 3+ stops.

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