Mechanical alloying (MA) has been proven to be an energy-efficient synthetic route for the development of high-performance thermoelectric (TE) materials. Higher Manganese Silicide (HMS) phases of the general formula Mn(Si_1−xAl_x)_1.75 (0 ≤ x ≤ 0.05) were prepared by MA implementing a short-time ball-milling process. Powder XRD and SEM analysis were carried out to validate the HMS phases, while small amounts of the secondary phase, MnSi, were also identified, especially for the Al-doped products. Electrical transport properties measurements showed that Al substitution causes an effective hole doping. A remarkable increase in electrical conductivity is observed for the Al-doped phases, while the corresponding reduction in the Seebeck coefficient is indicative of the increase in carrier density. Despite the small percentages of MnSi detected in Al-doped phases, an improvement in TE efficiency is achieved in the series Mn(Si_1−xAl_x)_1.75 (0 ≤ x ≤ 0.05). The 2.5% Al-doped phase exhibits a maximum figure-of-merit (ZT) of 0.43 at 773 K. Moreover, in an effort to utilize recycled silicon byproducts from photovoltaic (PV) manufacturing, Al-doped phases are developed by MA using two types of Si kerf. The two kerf-based products exhibit lower TE efficiencies, due to the increased amounts of the metallic MnSi phase.