Recently, several studies have revealed that the thermal annealing process induces intermixing at the interfaces of multilayered solution-processed organic light emitting diodes (OLEDs) and enhances their device performance. Depth profiling measurements, such as neutron reflectometry, have meticulously shown that significant intermixing occurs when the annealing temperature exceeds the glass transition temperature (Tg) of OLED materials. However, electrical characterization to unveil the physical origins of the correlation between interfacial characteristics and device performance is still lacking. Here, we introduce impedance spectroscopy (IS) analysis to examine the thermally induced modifications of charge carrier dynamics in a solution-processed bilayer OLED, consisting of an emission layer and an electron transporting layer (ETL). The characteristic relaxation frequency and capacitance extracted from the capacitance-frequency spectra of the OLEDs thermally annealed at varying temperatures were utilized to separately assess the conductance of the ETL and interfacial carrier accumulation, respectively. The results show that the improved charge transport of the ETL upon thermal annealing is mainly responsible for the performance enhancement since annealing the OLEDs at a temperature above the Tg of the ETL, at which significant intermixing occurs, promotes non-radiative trap-assisted recombination and thereby deteriorates the current efficiency. The proposed IS analysis exhibits that IS can separately probe the charge transport, interfacial charge accumulation and recombination process which are crucial for accurate analysis of charge carrier dynamics in solution-processed OLEDs and can thus be utilized to identify the key factors limiting the device performance.