Thanks for the query.
Plan B will work if it is taken within 72 hours of the unprotected sex, irrespective of whether you are ovulating or not. As the interval between the sex which was last done and the time of consumption of plan B increases, the effectiveness of the contraception decreases. Always remember there are 0.5 to 1% chances of failure. There is no contraception which is 100 % effective.
Hope this helped
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