Conventional fluorescent WOLEDs generate white light by incomplete energy transfer but face challenges in precisely controlling energy transfer and improving device efficiency due to the maximal utilization of 25% singlet excitons. In this study, two newly developed excited‐state intramolecular proton transfer (ESIPT) fluorophores emit orange and white light. These fluorophores utilize excitons efficiently (70–88%) via high‐level reverse intersystem crossing (hRISC) exclusively in the keto form and in both isomers (enol/keto), respectively. The white emitter, with comparable dual emissions, enables the fabrication of color‐stable cold‐white single‐emitter OLED with a CRI of 74 and maximum external quantum efficiency (EQE) of up to 5.60%. The orange emitter, when combined with a sky‐blue TADF fluorophore, creates non‐energy‐transferred single‐emitting‐layer (SML) high‐performance cold‐ and pure‐white WOLEDs with CIE coordinates of (0.26, 0.35) and (0.32, 0.32), and maximum EQEs of 13.34% and 9.66%, respectively. Importantly, these complementary‐color WOLEDs demonstrate high reproducibility, offering advantages for industrial batch fabrication. Thus, this research presents a route to achieve cost‐effective mass production of simple‐structured and high‐efficiency WOLEDs.