Multiprotocol Label Switching (MPLS) is an emerging technology which ensures the reliable delivery of the Internet services with high transmission speed and lower delays. The key feature of MPLS is its Traffic Engineering (TE), which is used for effectively managing the networks for efficient utilization of network resources. Due to lower network delay, efficient forwarding mechanism, scalability and predictable performance of the services provided by MPLS technology makes it more suitable for implementing real-time applications such as voice and video. In this thesis performance of Voice over Internet Protocol (VoIP) application is compared between MPLS network and conventional Internet Protocol (IP) network. OPNET modeler 14.5 is used to simulate the both networks and the comparison is made based on some performance metrics such as voice jitter, voice packet end-to-end delay, voice delay variation, voice packet sent and received. The simulation results are analyzed and it shows that MPLS based solution provides better performance in implementing the VoIP application. In this thesis, by using voice packet end-to-end delay performance metric an approach is made to estimate the minimum number of VoIP calls that can be maintained, in MPLS and conventional IP networks with acceptable quality. This approach can help the network operators or designers to determine the number of VoIP calls that can be maintained for a given network by imitating the real network on the OPNET simulator.