Microvolume blood collection technologies are of intense interest in healthcare. Whereas dried blood spots collect all the blood components, the majority of clinical tests are performed on the noncellular, plasma component of blood. Thus, there is a critical need for a robust plasma‐collecting device, which can stabilize biomarkers of interest for clinical analysis. A dried plasma spot, which consists of a separation membrane for removing red blood cells (RBC) while avoiding cell lysis and an absorbing layer for collecting and stabilizing plasma biomarkers after separation may provide such a solution. We report a novel use of electrospun polyacrylonitrile membranes to achieve a very promising separation of RBCs with near‐zero retention of human albumin protein (MW: 66.5 kDa). Physicochemical qualities of the separation membranes can be further optimized through doping and refinement of electrospinning conditions. The membranes may have future potential in microvolume sample collecting applications.