One essential requirement for a modern Smart Grid is continuous monitoring of the grid variables. This task is efficiently achieved using self-powered electronic devices deployed throughout the grid network. Within the vicinity of the grid power lines, the high voltages of these lines can provide a source of energy for such loads using capacitive coupling. This is known as Electric-Field Energy Harvesting (EFEH). However, the reported strategies that use this principle have not explored how to maximise their power transfer, which is essential for practical systems since the available energy from EFEH is invariably quite small. In this paper, a novel approach for optimum energy harvesting is proposed using the parasitic capacitance of medium-voltage power line insulators. A follow-on power electronic conversion system is then used to maintain the load conditions that maximise the extracted energy. The system performance has been analysed using theoretical studies and computer simulations to identify the operating conditions that maximise the extracted energy. Results obtained so far suggest that up to 100 mW can be harvested from 22 kV grid feeders, using only the capacitive coupling that exists between the line insulator harvester and the feeder conductor.