Fly ash (FA) is a waste product generated in huge amounts by coal-fired electric and steam-generating plants. As a result, the use of FA alone or in conjunction with other materials is an intriguing study topic worth exploring. Herein, we used FA waste in conjunction with titanium oxide (TiO2) to create (FA-TiO2) nanocomposites. For the first time, a cathodic polarization pre-treatment regime was applied to such nanocomposites to efficiently produce hydrogen from an alkaline solution. The FA-TiO2 hybrid nanocomposites were prepared by a straightforward solvothermal approach in which the FA raw material was mixed with titanium precursor in dimethyl sulfoxide (DMSO) and refluxed during a given time. The obtained FA-TiO2 hybrid nanocomposites were fully characterized using various tools and displayed a cenosphere-like shape. The synthesized materials were tested as electrocatalysts for the hydrogen evolution reaction (HER) in 0.1 M KOH solution in the dark, employing various electrochemical techniques. The as-prepared (unactivated) FA-TiO2 exhibited a considerable HER electrocatalytic activity, with an onset potential (EHER) value of −144 mV vs. RHE, a Tafel slope (−bc) value of 124 mV dec−1 and an exchange current density (jo) of ~0.07 mA cm−2. The FA-TiO2′s HER catalytic performance was significantly enhanced upon cathodic activation (24 h of chronoamperometry measurements performed at a high cathodic potential of −1.0 V vs. RHE). The cathodically activated FA-TiO2 recorded HER electrochemical kinetic parameters of EHER = −28 mV, −bc = 115 mV dec−1, jo = 0.65 mA cm−2, and an overpotential η10 = 125 mV to yield a current density of 10 mA cm−2. Such parameters were comparable to those measured here for the commercial Pt/C under the same experimental conditions (EHER = −10 mV, −bc = 113 mV dec−1, jo = 0.88 mA cm−2, η10 = 110 mV), as well as to the most active electrocatalysts for H2 generation from aqueous alkaline electrolytes.