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Can we write the UPSC exam in the general category for the first attempt and change to OBC for the next year/next time?

Yes you can.

A good friend of mine, who is currently in the Indian Corporate Law service, wrote the exam the first time without taking reservation. He got a rank with which he could have got IFS if he had opted for reservation.

He is writing the exam this year (2016) in the reserved category. It is your choice to forego or avail of the benefit.