Semiconductor light-emitting diodes (LEDs), especially GaN-based heterostructures, are widely used in light illumination. The lack of inversion symmetry of wurtzite crystal structures and the lattice mismatch at heterointerfaces cause large polarization fields with contributions from both spontaneous polarization and piezoelectric polarization, which in turn results in obvious quantum confined stark effect. It is possible to alleviate this effect if the local electrostatic fields and band alignment induced charge redistribution can be quantitatively determined across the heterostructures. In this Concept, the applications of electron holography to investigate semiconductor LEDs are summarized. Following the off-axis electron holography scheme, the GaN-based LED heterostructures including InGaN/GaN-based quantum wells, other GaN-based quantum wells, and other forms of GaN-based LED materials are discussed, focusing on the local potential drops, polarization fields, and charge distributions. Moreover, GaAs-based LED heterostructures are briefly discussed. The in-line electron holography scheme emphasizes the capability of large area strain mapping across LED heterostructures with high spatial resolution and accuracy, which is combined with quantitative electrostatic measurements and other advanced transmission electron microscopy characterizations to provide an overall nanometer scale perspective of LED devices for further improvement in their electric and optical properties.