In general, a transfer to a new job location 65 miles away, would make you eligible for unemployment benefits. The unemployment examiner will look at whether a transfer of 65 miles requiring such a commute is reasonable in your area. Such a distance would probably qualify as too far, as it is based on a reasonable commuting distance.
If the distance were less, such as 30-40 miles, then the question would be closer. However, it is recommended that you immediately consult with a qualified employment lawyer in your area to ensure that in fact you would likely be eligible for benefits. This is because local conditions and state case law could affect the examiner's decision.