Herein, the photocatalytic degradation of the Congo Red (CR) and Crystal Violet (CV) dyes in an aqueous solution were discussed in the presence of an indium(III) oxide (In2O3) as optical catalyst efficiency. The caproate bidentate indium(III) precursor complex has been synthesized and well interpreted by elemental analysis, molar conductivity, Fourier transform infrared (FT-IR), UV-Vis, and thermogravimetric (TGA) with its differential thermogravimetric (DTG) studies. The microanalytical and spectroscopic assignments suggested that the associated of mononuclear complex with 1:3 molar ratio (M3+:ligand). Octahedral structure is speculated for this parent complex of the caproate anion, CH3(CH2)4COO− ligand. The In2O3 NPs with nanoscale range within 10–20 nm was synthesized by a simple, low cost and eco-friendly method using indium(III) caproate complex. Indium oxide nanoparticles were formed after calcination of precursor in static air at 600°C for 3 hrs. The structural, grain size, morphological and decolorization efficiency of the synthesized NPs were characterized using the FT-IR, X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX) and transmission electron microscopy (TEM) analyses. It was worthy mentioned that the prepared In2O3 NPs showed a good photodegradation properties against CR and CV organic dyes during 90 min.