We have systematically studied the evolution of the photoluminescence(PL) tuning of porous silicon(PS) by electrochemical etching in various mixed electrolytes. The electrolytes employed as an etchants were mixtures of HF:CH3COOH:HNO3:C2H5OH solutions where the composition ratios (%) were varied from 10:1.98:0:88.02 to 10:1.98:8.4:79.62 under constant concentration of HF and CH3COOH with a total volume of 100 ml. Changes in the surface morphology of the samples caused by variations in the etching process were investigated by scanning electron microscopy (SEM) and atomic force microscopy (AFM). After samples are etched in various mixed electrolytes, FTIR analyses show that there is the non-photoluminescent state and the photoluminescent state simultaneously. The PL spectra show the PL tuning in the ranging from 560 to 700 nm with the increase of HNO3 concentration. An analysis of the subsequent PL relaxation mechanism was carried out by time-correlated single photon counting (TCSPC) method. Based on experimental results, it is assumed that a red shift of the main PL peak position is related to the HNO3 activated formation of silicon oxygen compounds. Therefore, the use of electrolyte mixtures with composition ratios can be obtained adequate and reproducible results for PL tuning.