Enhancing device efficiencies of the blue and white light-emitting electrochemical cells (LECs) is realized by employing substrates with embedded diffusive layers containing scattering TiO2 nanoparticles (NPs). The diffusive layers can eliminate the influence of microcavity effect on the output electroluminescence (EL) spectrum and recover the intrinsic EL spectrum of the emissive layer. The emission zone positions of the blue and white LECs are estimated by fitting the measured EL spectra with the simulated EL spectra based on precisely tuned emission zone positions. Incorporating red-emitting guest dopant in the white LEC results in shifted emission zone toward the cathode due to enhanced electron trapping. The external quantum efficiency (EQE) of the blue and white LECs employing proper diffusive substrates can be enhanced by 260 and 210%, respectively. The maximal EQE (power efficiency) of the blue and white LECs reach 35.4% (83.4 lm W−1) and 22.0% (41.6 lm W−1), respectively. These promising device efficiencies confirm the potential applications for the proposed diffusive substrates in enhancing light extraction from LECs. In addition, adjusting the effective refractive index of the diffusive layer has distinct effect on different EL emission color. With well confined optical field of blue EL in indium tin oxide layer, lower effective refractive index of the diffusive layer results in higher refractive index difference between the scattering TiO2 NPs and the host medium, rendering higher scattering efficiency and more light extraction. In contrast, higher effective refractive index of the diffusive layer leads to unguided red EL extending into the diffusive layer and more light can be outcoupled. These results show that the effective refractive index of the diffusive layer should be judiciously chosen according to the emission color of EL to be extracted.