In this study, we shed light on the coupling between voltage (V) and tip-to-collector distance (T) in polymer electrospinning. First, an operating map in the V-T plane – with the potential to facilitate real-time control – reveals four electrospinning regimes including a newly identified rotational regime that serves as a transition from the cone-jet to the multi-jet regime. Next, across experiments in which V and T are independently varied, we image and comprehensively investigate regime-specific cone and jet dynamics using quantifiable and universally recognizable features. Our results demonstrate for the first time that theoretical potential drop (V/T) ─ although crucial in determining electrospinning outcomes ─ is not a fundamental V-T coupling parameter. Further, the nature of coupling is shown to dynamically vary with specific V and T combinations, with correlations indicating stronger dependence of cone/jet features on V than on T. Significantly, small changes to the collector position orchestrates regime transitions at the needle tip despite the large separation distance, although the effects of V dominate at large T values. Supporting simulations implicate the combined roles of effective field strength, charge density and field line distribution near the cone apex as critical factors influencing V-T coupling. © 2020 Elsevier Ltd