In general, OPM Box 5 is health insurance deduction only, but you should contact them if you are not sure. See Get your 1099-R tax form (Look for Get your annual sum of payment)
Employee contributions occur when you contribute to your own retirement account as an after tax contribution. When you take the money out, it may be tax-free. This could also represent the basis you have in your designated Roth account. The designated Roth after tax contributions may be taken out tax-free.
It could also be the portion of your insurance premiums you paid that can be taken out tax-free. Another entry could be the nontaxable portion of a charitable gift annuity.
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