Thermally Activated Delayed Fluorescent (TADF) luminophores offer the potential to achieve 100% Internal Quantum Efficiency (IQE) by harvesting both singlet and triplet excitons via reverse intersystem crossing from T₁ to S₁. This class of molecules has therefore been embraced in the pursuit of cheaper and more efficient electrochemiluminescent (ECL) labels. The present study explores how tuning the electron-donating (D) and -accepting (A) strengths of peripheral substituents affects the ECL emission of mono- and dicyanoarene-based TADF dyes. To this end, we synthesized two series of TADF compounds, independently manipulating electron donors and acceptors by (i) halogenating electron-rich diphenylamine moieties, or (ii) mono- or di-substituting the electron-poor cyanoarene core with either fluorine or imidazole. Through a comparative analysis, we elucidate the role of each substituent in shaping the photophysics of the investigated luminophores. Despite only achieving a relative Φ_ECL as high as 1.27%, this framework identifies several molecular features that boost the ECL efficiency to pave the way for designing highly efficient TADF-based ECL emitters. Ultimately, imidazole substituents are exploited as a platform for functionalization with triethylene glycol units. The resulting water-soluble TADF luminophores are characterized under conditions usual to commercial ECL bioanalysis, proving their potential as a cost-effective alternative replacement to [Ru(bpy)₃]²⁺ in clinical diagnostic.