We present a novel method for accurately splitting ionic samples at microchannel bifurcations. We leverage isotachophoresis (ITP) to focus and transport sample through a one-inlet, two-outlet microchannel bifurcation. We actively control the proportion of splitting by controlling potentials at end-channel reservoirs (and thereby controlling the current ratio). We explore the effect of buffer chemistry and local electric field on splitting dynamics and propose and validate a simple Kirchoff-type rule controlling the split ratio. We explore the effects of large applied electric fields on sample splitting and attribute a loss of splitting accuracy to electrohydrodynamic instabilities. We propose a scaling analysis to characterize the onset of this instability. This scaling is potentially useful for other electrokinetic flow problems with self-sharpening interfaces