Copper iodide, an environmentally friendly material abundant in nature, holds great significance for room temperature thermoelectric (TE) applications owing to its high Seebeck coefficient and optical transparency. However, to fully unlock its thermoelectric potential and match the performance of conventional TE materials, there is a need to further enhance its electrical conductivity. In this study, we have successfully synthesized nano-crystalline powders of both undoped and aluminium-doped CuI at room temperature using the chemical precipitation method in an ethanol medium. The concentration of aluminium dopant has been optimized to maximize TE performance. At 400 K, the highest TE power factor and figure of merit achieved are 79 μW m-1 K-2 and 0.08, respectively, for CuI doped with 0.1 mol% Al. This enhancement in TE properties can be attributed to the increased carrier density resulting from aluminium doping. The impact of aluminium doping on the temperature-dependent thermal conductivity has been investigated, and the findings are explained by the decay mechanism of optical phonons, supported by the anharmonic phonon coupling theory. Our work delves into the evolution of structural, thermal, optical, and TE properties of CuI upon aluminium (Al) doping. The results provide valuable insights into the future application of CuI in transparent thermoelectric and optoelectronic fields.