Measuring the polydisperse beam of charged species emitted by an electrospray device requires accurate measurements of current. Secondary species emission (SSE) caused by high-velocity nanodroplet or molecular ion impacts on surfaces contributes to substantial uncertainty in current measurements. SSE consists of both positive and negative species; hence, mitigating measurement uncertainty requires different considerations other than plasma diagnostic techniques. The probe and analysis methods described herein distinguish between current contributions from positive SSE, negative SSE, and primary species. Separating each contribution provides positive and negative SSE yield measurements and corrected current measurements that reflect the true primary current. Sources of measurement uncertainty in probe design are discussed, along with appropriate mitigation methods. The probe and analysis techniques are demonstrated on an ionic liquid electrospray operating in a droplet emission mode to obtain an angular distribution of positive and negative SSE yields for an ionic liquid electrospray.