In recent years, silicon nanostructures have been investigated extensively for their potential use in photonic and photovoltaic applications. So far, for silicon quantum dots embedded in SiO₂, control over inter-dot distance and size has only been observed in multiple bilayer stacks of silicon-rich oxides and silicon dioxide. In this work, for the first time the fabrication of spatially well-ordered Si quantum dots (QDs) in SiO₂ is demonstrated, without using the multilayer approach. This ordered formation, confirmed with TEM micrographs, depends on the thickness of the initially deposited sub-stoichiometric silicon oxide film. Grazing incidence x-ray diffraction confirms the crystallinity of the 5 nm QDs while photoluminescence shows augmented bandgap values. Low-temperature current–voltage measurements demonstrate film thickness and order-dependent conduction mechanisms, showing the transition from temperature-dependent conduction in randomly placed dots to temperature-independent tunnelling for geometrically ordered nanocrystals. Contrary to expectations from dielectric materials, significant conduction and photocarrier generation have been observed in our Si QDs embedded in SiO₂ demonstrating the possibility of forming initial film-thickness-controlled conductive films. This conduction via the silicon quantum dots in thick single layers is a promising result for integration into photovoltaic devices.