Silica multi-layer stacks have been designed with the aim to provide broadband antireflective (AR) properties for glass components in concentrated photovoltaic (CPV) application. Silica porous coatings were grown by combining acid-catalyzed sol-gel route and evaporation induced self-assembly (EISA) method with four types of organic/inorganic systems. Sols were prepared using tetraethylorthosilicate (TEOS) as inorganic precursor assembled with two di-block copolymers, one tri-block copolymer and one cationic surfactant as organic templates. Optical properties were characterized by ellipsometry and spectrophotometry while the material structure was analyzed by environmental ellipsometric porosimetry (EEP) and atomic force microscopy (AFM). The concentration of inorganic and organic phases was optimized and a broadband AR bi-layer stack was obtained providing a 7.2% (under the reference AM1.5 solar spectral irradiance) increase in transmittance over bare glass in the wavelength range 300–2000 nm when coated on both sides. This work was supported by the Basque Government for EMAITEK 2017 program as well as the ELKARTEK projects FRONTIERS-2 (Contract no. KK2016-00093 ) and FRONTIERS-3 (Contract no. KK2017-00096 ) This work has received funding from the European Union's Horizon 2020 Research and Innovation Programme within the project CPVMatch under Grant agreement no. 640873 . The authors are solely responsible for the content of this work and it only reflects the author's view. The authors thank ICV-CSIC, Yolanda Castro and Alicia Durán for ellipsometry and EEP measurements.