Positively and negatively charged polyelectrolytes, namely, Poly(diallyldimethylammonium chloride) and Poly(styrene sulfonate), respectively, were employed to disperse and deploy negatively charged quantum dots on an otherwise passive metamaterial structure with a resonant frequency of 0.62 THz, by employing a layer-by-layer, self-assembly scheme. Upon exposure to a UV source with a wavelength of 365 nm the amplitude modulation was observed to increase with increases in the number of deposited bi-layers, until a modulation maximum of 2.68% was recorded enabling an all-optical, dynamically reconfigurable metamaterial geometry. Furthermore, amplitude modulation was subsequently observed to decrease with further increases in the number of layers employed due to quenching and shadowing effects. The experimental observations reported herein will enable the utilization of all-optical reconfigurable THz devices for communication and data transmission applications.