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• The onset and termination electric potential to form the steady cone-jet electrospray increase as conductivity increasing. • The lower and upper limitation of liquid flowrate to form the steady cone-jet electrospray decrease as conductivity increases. • The varicose instability can transform into whipping instability as the electrical conductivity increasing. • The jet breakup instability transition mechanism is interpreted by theoretical analysis. • The whipping to similar micro-dripping instability can be observed for EG with higher conductivity. In present work, the effect of the electrical conductivity on the steady cone-jet electrospray are experimentally investigated, where the operating diagram and the jet breakup instability are extensively examined. A hemispherical tube is employed as spraying nozzle severed as high electric potential electrode in a needle-plated electrode configuration compared to the common and sheathed tubes. The cone-jet electrospray is visualized by a high-resolution camera and extensively analyzed offline. The aqueous solution in ethanol, Diethyleneglycol (DEG) and Ethylene glycol (EG) are atomized with varied electrical conductivity under different high electric potentials and flowrates. Experimental results indicate that the cone-jet electrospray can operate in the certain ranges of operating parameter for all types of capillaries. The operating diagram for the hemispherical tube is significantly broader than other tubes because of various electric field strength distribution. The onset electric potential to determine a steady cone-jet electrospray gradually increases and the termination value also increases as the electrical conductivity increases. The lower and upper flowrate to form a steady cone-jet electrospray also increase as the electrical conductivity increases. The jet breakup instability can transit from varicose to whipping due to low the reference flow rate as electrical conductivity increases, which is agreement with theoretical analysis. In particular, for EG, the transition from whipping to similar micro-dripping is observed as the electrical conductivity increases, while the transition also occurs as flowrate increases for EG with higher electrical conductivity. The increase in the electrical conductivity and flowrate elongates the cone due to EHD body force, which causes the electric field varying, further resulting in the difference in jet breakup instability. Moreover, the electrical conductivity also plays an important role in jet breakup length. The instability variation of jet with conductivity (DEG), q V =1000 nL/s, ϕ =8.00 kV (Hemispherical nozzle with D o =0.70mm); The variation with liquid flow rate of EG with higher conductivity (K =8.5 × 10−4 s/m, ϕ =10.20 kV, (Hemispherical nozzle with D o =0.70mm) [Display omitted] [ABSTRACT FROM AUTHOR]