The semiconductor industry is the backbone of modern electronics, driving advancements in computing, communication, and artificial intelligence through relentless scaling and precision in material engineering. As the thickness of chips is reducing, there is a need to innovate new methodologies. This work presents an in-depth investigation of alcohol-based co-reactants in atomic layer deposition (ALD), combining density functional theory (DFT) simulations with experimental validation. Motivated by the limitations of conventional oxidants such as H₂O, the study explores the mechanistic behavior of primary, secondary, and tertiary alcohols on reactive metal surfaces. Possible mechanisms for allyl alcohols have also been explored using DFT. Key reaction pathways such as alkoxy formation, β-H elimination, and sigma tropic rearrangement are analyzed using DFT to quantify activation energies and thermodynamics. Experimental ALD growth studies, supported by QCM and surface analysis, confirm the trends predicted computationally. Notably, tertiary butanol and 2-methyl-3-buten-2-ol (MBO) display optimal kinetic and thermodynamic profiles, enabling controlled and selective film growth. The findings demonstrate that combining theory and experiment not only reveals underlying reaction mechanisms but also enables rational co-reactant design for area-selective and low-temperature ALD applications.