Usually, as part of a workers’ compensation settlement, the employer will want a resignation as part of the deal. Your attorney will have to bargain for favorable language if you wish to seek UC benefits.
You should discuss the case Lee v. Unemployment Compensation Board of Review with your attorney. In this case, the injured worker gave both a resignation and a release as part of her workers’ compensation settlement. Following the approval of the settlement, the Claimant filed for unemployment compensation benefits.
Benefits were initially granted but The Unemployment Compensation Board of Review reversed, finding the injured worker not eligible for unemployment compensation benefits. Upon further appeal, this was affirmed by the Commonwealth Court of Pennsylvania. If your resignation is "voluntary" you may not be eligible for UC benefits.