Electrohydrodynamic jet (e-jet) printing is a modern and decent fabrication method widely used to print high-resolution versatile microstructures with features down to 10 μm. It is currently difficult to break nanoscale resolution (<100 nm) due to limitations of fluid properties, voltage variations, and needle shapes. This paper presents developments in drop-on-demand e-jet printing based on a phase-field method using a novel combined needle and straight electrode to print on a flexible PET substrate. Initially, the simulation was performed to form a stable cone jet by coupling an innovative straight electrode parallel to a combined needle that directs the generation of droplets at optimized parameters, such as f = 8.6 × 10−10 m3s−1, Vn = 9.0 kV, and Vs = 4.5 kV. Subsequently, printing experiments were performed using optimized processing parameters and all similar simulation conditions. Microdroplets smaller than 13 μm were directly printed on PET substrate. The model is considered unique and powerful for printing versatile microstructures on polymeric substrates. The presented method is useful for MEMS technology to fabricate various devices, such as accelerometers, smartphones, gyroscopes, sensors, and actuators.