The multi-controller placement problem (MCPP) represents one of the most challenging issues in software-defined networks (SDNs). High-efficiency and scalable optimized solutions can be achieved for a given position in such networks, thereby enhancing various aspects of programmability, configuration, and construction. In this paper, we propose a model called simulated annealing for multi-controllers in SDN (SA-MCSDN) to solve the problem of placing multiple controllers in appropriate locations by considering estimated distances and distribution times among the controllers, as well as between controllers and switches (C2S). We simulated the proposed mathematical model using Network Simulator NS3 in the Linux Ubuntu environment to extract the performance results. We then compared the results of this single-solution algorithm with those obtained by our previously proposed multi-solution harmony search particle swarm optimization (HS-PSO) algorithm. The results reveal interesting aspects of each type of solution. We found that the proposed model works better than previously proposed models, according to some of the metrics upon which the network relies to achieve optimal performance. The metrics considered in this work are propagation delay, round-trip time (RTT), matrix of time session (TS), average delay, reliability, throughput, cost, and fitness value. The simulation results presented herein reveal that the proposed model achieves high reliability and satisfactory throughput with a short access time standard, addressing the issues of scalability and flexibility and achieving high performance to support network efficiency.