This study achieved the decoration of poly-3-methyl aniline (P3MA) with As2O3–As(OH)3 using K2S2O8 and NaAsO2 on the 3-methyl aniline monomer. This resulted in a highly porous nanocomposite polymer composite with wide absorption optical behavior, an average crystalline size of 22 nm, and a 1.73 eV bandgap. The photoelectrode exhibited a great electrical response for electroanalytical applications, such as photon sensing and photodiodes, with a Jph of 0.015 mA/cm2 and Jo of 0.004 mA/cm2. The variable Jph values ranged from 0.015 to 0.010 mA/cm2 under various monochromatic filters from 340 to 730 nm, which demonstrates high sensitivity to wavelengths. Effective photon numbers were calculated to be 8.0 × 1021 and 5.6 × 1021 photons/s for these wavelength values, and the photoresponsivity (R) values were 0.16 and 0.10 mA/W, respectively. These high sensitivities make the nanocomposite material a promising candidate for use in photodetectors and photodiodes, with potential for commercial applications in highly technological systems and devices. Additionally, the material opens up possibilities for the development of photodiodes using n- and p-type materials.