Microwave sensors have recently been introduced as high-temporal resolution sensors, which could be used in the contactless monitoring of artery pulsation and breathing. However, accurate and efficient signal processing methods are still required. In this paper, the matrix pencil method (MPM), as an efficient method with good frequency resolution, is applied to back-reflected microwave signals to extract vital signs. It is shown that decomposing of the signal to its damping exponentials fulfilled by MPM gives the opportunity to separate signals, e.g., breathing and heartbeat, with high precision. A publicly online dataset (GUARDIAN), obtained by a continuous wave microwave sensor, is applied to evaluate the performance of MPM. Two methods of bandpass filtering (BPF) and variational mode decomposition (VMD) are also implemented. In addition to the GUARDIAN dataset, these methods are also applied to signals acquired by an ultra-wideband (UWB) sensor. It is concluded that when the vital sign is sufficiently strong and pure, all methods, e.g., MPM, VMD, and BPF, are appropriate for vital sign monitoring. However, in noisy cases, MPM has better performance. Therefore, for non-contact microwave vital sign monitoring, which is usually subject to noisy situations, MPM is a powerful method.