When a dilute polymer solution experiences capillary thinning, it forms an almost uniformly cylindrical thread, which we study experimentally. In the last stages of thinning, when polymers have become fully stretched, the filament becomes prone to instabilities, of which we describe two: a novel breathing instability, originating from the edge of the filament, and a sinusoidal instability in the interior, which ultimately gives rise to a blistering pattern of beads on the filament. We describe the linear instability with a spatial resolution of 80 nm in the disturbance amplitude. For sufficiently high polymer concentrations, the filament eventually separates out into a "solid" phase of entangled polymers, connected by fluid beads. A solid polymer fiber of about 100 nm thickness remains, which is essentially permanent.