A high-performance monolithic photovoltaic- thermoelectric hybrid generator with a photothermal conversion layer is introduced. The layer, a thin acrylic film dyed with black colored AZO dye, effectively absorbs photons in the near-infrared region. The AZO dye supports an exothermic reaction through nonradiative relaxation. The hybrid generator was fabricated through monolithic integration. A thermoelectric (TE) module was fabricated directly on the back surface of the photovoltaic (PV) module without using the ceramic substrate typically employed in conventional TE modules, so that thermal resistance between the PV module and TE module could be minimized. The 51.35 cm(2) fabricated hybrid generator showed a power conversion efficiency of about 22.5% with an open-circuit voltage of 0.94 V and a maximum power of 1.15 W under standard AM 1.5G illumination. The hybrid power generator with the photothermal conversion layer showed about 40% higher output power compared to the control PV only, about 16% higher than an acrylic control film, and about 7.4% higher than a common black dyed interface layer.