Porous silica anti-reflection (AR) films are of importance in solar cells' photon harvest. However, the usual utilized method to fabricate AR films is the two-step method since the formation of porous silica NPs (first step) and silica coating sol (second step) always require chemical systems at distinct pH values. To reduce the complexity of the process, we choose cationic emulsion as an approach to produce the porosity and propose a convenient one-step route to get high-performance antireflective films. A single layer SiO2 anti-reflective (AR) film with high optical transmittance up to 97.5% at 740 nm was fabricated from composite sol that was made from cationic emulsion nanolatex and tetraethylorthosilicate under acid catalysis condition. After calcination, the transmittance of AR coated glasses still held the transmittance of 96% at 550 nm. Composited with SiO2, Al2O3, or TiO2 sol binders, the transmittance of AR coated glasses could be recovered as high as 97.9% at 650 nm and the pencil hardness was further strengthened up to 6H. The composite sol can keep stable at least one month at ambient temperature without any visible precipitation. Therefore, the proposed method is promising for developing high-performance AR films effectively and economically.