Electricity is a vital factor underlying modern living standards, but there are many developing countries with low levels of electricity access and use. We seek to systematically identify the crucial elements underlying transitions toward greater electrification in developing countries. We use a cross-sectional regression approach with national-level data up to 2012 for 135 low- and middle-income countries. The paper finds that the effectiveness of governments is the most important governance attribute for encouraging the transition to increased electrification in developing countries, on average. The results add to the growing evidence on the importance of governance for development outcomes. Donors seeking to make more successful contributions to electrification may wish to target countries with more effective governments.