The development of eco-friendly solution-processed PHOLEDs (s-PHOLEDs) is a significant issue due to the toxicity of halogenated solvents. However, high-performance s-PHOLEDs have predominantly relied on halogenated solvents, owing to their superior ability to dissolve organic materials and facilitate high-quality film formation in the EMLs. To advance the development of eco-friendly s-PHOLEDs, several criteria are required to solve; the development of emitters and host materials having high solubility in eco-friendly solvents and the establishment of optimal conditions for achieving high-quality films, including uniformity, thickness, and morphology. Herein, we developed eco-friendly s-PHOLEDs using a novel green phosphorescent emitter, MECF-pop, and a new thermally cross-linkable hole transport material, C2DPACzPVB, using 2-methylanisole (2-MA) as a food additive solvent for device fabrication. We utilized an exciplex forming mixed hosts system consisting of TCTA as a hole transport type material and TPBi as an electron transport type material. Interestingly, the variation of exciplex formation was observed in the EMLs due to the changed dispersion of TCTA and TPBi according to film-forming conditions. The optimized eco-friendly s-PHOLEDs using chlorobenzene and 2-MA showed maximum external quantum efficiencies of 26.4 and 22.7% and current efficiencies of 94.8 and 81.2 cd A^-1, respectively.