The doping level dependence of thermoelectric properties of delafossite CuAlO2 has been investigated in the constant scattering time (τ) approximation, starting from the first principles of electronic structure. In particular, the lattice parameters and the energy band structure were calculated using the total energy plane-wave pseudopotential method. It was found that the lattice parameters of CuAlO2 are a = 2.802 Å and c = 16.704 Å, and the internal parameter is u = 0.1097. CuAlO2 has an indirect band gap of 2.17 eV and a direct gap of 3.31 eV. The calculated energy band structures were then used to calculate the electrical transport coefficients of CuAlO2. By considering the effects of doping level and temperature, it was found that the Seebeck coefficient S(T) increases with increasing acceptor doping (Ad) level. The values of S(T) in our experiments correspond to an Ad level at 0.262 eV, which is identified as the Fermi level of CuAlO2. Based on our experimental Seebeck coefficient and the electrical conductivity, the constant relaxation time is estimated to be 1 × 10−16 s. The power factor is large for a low Ad level and increases with temperature. It is suggested that delafossite CuAlO2 can be considered as a promising thermoelectric oxide material at high doping and high temperature.