A highly efficient homogeneous catalyst system for the production of CH₃OH from CO₂ using pentaethylenehexamine and Ru-Macho-BH (1) at 125–165 °C in an ethereal solvent has been developed (initial turnover frequency = 70 h^-1 at 145 °C). Ease of separation of CH₃OH is demonstrated by simple distillation from the reaction mixture. The robustness of the catalytic system was shown by recycling the catalyst over five runs without significant loss of activity (turnover number > 2000). Various sources of CO₂ can be used for this reaction including air, despite its low CO₂ concentration (400 ppm). For the first time, we have demonstrated that CO₂ captured from air can be directly converted to CH₃OH in 79% yield using a homogeneous catalytic system.