A first-principles study investigates how varying hydrofluoric acid (HF) concentrations affect the thermodynamic stability and electronic properties of Ti3C2Tx MXene surfaces with ordered and random ternary mixed terminations. The study reveals that OH-rich surfaces are thermodynamically stable and that the electrical conductivity of Ti3C2Tx is significantly influenced by OH concentration. Charge density difference and electron localization function analyses show significant electron localization at hydroxyl groups, leading to locally induced dipoles that create favorable reaction sites. The work function of Ti3C2Tx is highly tunable, with a predicted range of ΔΦ ~ 3.5 eV, depending on HF concentration. These findings suggest that the electronic and structural properties of Ti3C2Tx MXenes can be strategically tuned by adjusting HF concentration during etching. The study also highlights the importance of surface termination distribution in determining electronic properties, with ordered and random terminations showing similar thermodynamic stability. The work function is primarily a function of stoichiometry and is insensitive to surface termination distribution. The results provide insights into the fundamental characterization of Ti3C2Tx and a pathway for experimental tuning of material properties through HF concentration variation during MAX phase etching.A first-principles study investigates how varying hydrofluoric acid (HF) concentrations affect the thermodynamic stability and electronic properties of Ti3C2Tx MXene surfaces with ordered and random ternary mixed terminations. The study reveals that OH-rich surfaces are thermodynamically stable and that the electrical conductivity of Ti3C2Tx is significantly influenced by OH concentration. Charge density difference and electron localization function analyses show significant electron localization at hydroxyl groups, leading to locally induced dipoles that create favorable reaction sites. The work function of Ti3C2Tx is highly tunable, with a predicted range of ΔΦ ~ 3.5 eV, depending on HF concentration. These findings suggest that the electronic and structural properties of Ti3C2Tx MXenes can be strategically tuned by adjusting HF concentration during etching. The study also highlights the importance of surface termination distribution in determining electronic properties, with ordered and random terminations showing similar thermodynamic stability. The work function is primarily a function of stoichiometry and is insensitive to surface termination distribution. The results provide insights into the fundamental characterization of Ti3C2Tx and a pathway for experimental tuning of material properties through HF concentration variation during MAX phase etching.