Group V-VI-based metal-doped double chalcogenides are essential in thermoelectric and suitable optoelectronic devices. The present investigation is based on optimising various optical, structural, and electrical behaviours of quaternary As10Bi30Se30Te30 films through thermal annealing at different temperature scales. The structural study by X-ray diffraction (XRD) exhibited the presence of various Bi2Se3, Bi2SeTe2, and Bi2Te3 phases in the annealed films. The crystallinity gradually enhanced after the annealing process. The microstructural modifications in the material have been confirmed through the Raman spectra. The elemental confirmation was verified from the energy dispersive X-ray (EDX) spectra, whereas the cross-sectional scanning electron microscopy (SEM) view showed the annealing-induced modifications in the films. The granular structure in the films is seen from the surface morphology study. The reduction of the energy gap from 1.36 ± 0.002 eV to 1.26 ± 0.001 eV upon annealing induced the increment in refractive index from 3.08 to 3.15. With annealing, the non-linear refractive index varied from 4.341x10−10 esu to 5.218 x10−10 esu. This indicates the narrowing of the bandgap and enhancement in the non-linear optical response of the material after the annealing process. The 3rd-order nonlinear susceptibility is also increased by annealing, thus making it suitable for nonlinear device applications. Annealing-induced surface change in the material enhances its surface wettability and makes it more hydrophilic. The linear enhancement in photocurrent with the voltage is ohmic and makes it suitable for various optoelectronic applications.