The optimum annealing conditions of corn starch slurry were studied for RS4 type resistant starch production by phosphorylated cross-linking. When a corn starch slurry was cross-linked by using phosphate salts (STMP/STPP mixture) in the presence of 0.9%, 1.2% and 1.5% NaOH/st.ds, a high concentration of NaOH resulted in a rapid increase of the RS contents at the early reaction stage. However, similar RS contents were obtained after 12 h of cross-linking regardless of NaOH concentrations. The annealing treatment was conducted under various conditions such as pH between 2-10, temperature 40-60℃, time 0-14 h followed by phosphorylated cross-linking. The lower slurry pH was for the annealing treatment, the higher RS contents were obtained after cross-linking. When the slurry annealed for various period of time and temperature, a maximal amount of RS was formed after 2 h of annealing at 50℃ of annealing temperature of the starch slurry (pH 2.0). Therefore, an optimal annealing conditions at pH 2.0 and 50℃ for 2 h were proposed under the cross-linking conditions of sodium sulfate 10%/st.ds, NaOH1.2%/st.ds and 12 h of the reaction time. The RS contents were linearly increased with the increase of phosphate salt addition. The RS4 prepared under the optimal conditions contained RS 72.3% and its phosphorus content was 0.36%/st.ds, which was below the limit (0.4%/st.ds) of modified starch by Korea Food Additives Code.