About 1,300 members of the armed forces are covering for ambulance and border staff walkouts.
The MoD said the £20 payments would come out of the department's budget, and be made for each day of cover or training beforehand.
Ministers said they would help get people to A&E more quickly, but would not be allowed to drive ambulances under blue lights, go through red lights or break the speed limit. Shadow defence secretary John Healey said the government's "small gesture is better than nothing" but forces were "once again having to bail out Conservative ministers who are grinding our country to a halt".
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