Interface recombination in sub-μm optoelectronics has a major detrimental impact on devices’ performance, showing the need for tailored passivation strategies to reach a technological boost. In this article, SiOx passivation based substrates were de- veloped and integrated into ultrathin Cu(In,Ga)Se2 (CIGS) solar cells. This article aims to understand the impact of a passivation strategy, which uses several SiOx layer thicknesses (3, 8, and 25 nm) integrated into high-performance substrates (HPS). The experimental study is complemented with 3-D lumerical finite-difference time-domain and 2-D Silvaco ATLAS optical and electrical simulations, respectively, to perform a decoupling of optical and electronic gains, allowing for a deep discussion on the impact of the SiOx layer thickness in the CIGS solar cell performance. This article shows that as the passivation layer thickness increases, a rise in parasitic losses is observed. Hence, a balance between beneficial passivation and optical effects with harmful architectural constraints defines a threshold thickness to attain the best solar cell performance. Analyzing their electrical parameters, the 8-nm novel SiOx based substrate achieved a light to power conversion efficiency value of 13.2%, a 1.3% absolute improvement over the conventional Mo substrate (without SiOx).