This work presents simulation of jet break up in electrospray ionization using a microfluidic emitter. The emitter comprises a pointed carbon fiber located coaxial with a fused silica capillary of 360 microns OD and 75 microns ID, with its sharp tip extending 30 microns beyond the capillary terminus. The numerical model employs leaky-dielectric formulations for solving the electrodynamics and volume-of-fluid method for tracking the liquid-air interface. The existing leaky-dielectric model is modified to account for the presence of free charges inside the bulk of the liquid as well as at the interface. A small velocity perturbation is used at the capillary inlet to emulate the natural disturbance necessary for the jet break up. First, the model is validated by comparing model predictions with experimental results for a conventional emitter reported in literature. Then, it is applied to simulate the electrospray performance of the Carbon Fiber (CF) emitter including the Taylor cone and jet break up processes. Model predictions for CF emitter are compared with experimental results in terms of jet-length and current-flow characteristics. The influence of emitter geometry, operating conditions and liquid properties on the electrospray performance are investigated. Droplet diameter is correlated with flow rate and liquid properties and the correlation results are compared with that reported in literature.