To determine the optimal network architecture between the Basic Service Set, the Extended Service Set and the Independent Basic Service Set, this study established a new algorithm to assess Voice over Internet Protocol (VoIP) metrics of different IEEE 802.11 technologies. An important coefficient for each VoIP metric parameter has been invented to rank the different IEEE 802.11 standards and to identify the most efficient one for the VoIP application. The best overall network performance that offers good voice quality is ensured by determining the optimum network architecture and technology. Moreover, for the VoIP efficiency parameters, it meets the acceptance threshold values. This algorithm was implemented in different sizes of rooms ranging from 1 × 1 m to 10 × 10 m, and the number of nodes varied from 1 to 65. End to end delay, jitter, throughput and packet loss were the quality of service parameters used.