The calibration of Phasor Measurement Units (PMUs) consists of comparing Coordinated Universal Time (UTC) time-stamped phasors (synchrophasors) estimated by the PMU under test, against reference synchrophasors generated through a PMU calibrator. The IEEE Standard C37.118-2011 and its amendment (IEEE Std) describe compliance tests for static and dynamic conditions, and indicate the relative limits in terms of accuracy. In this context, the paper focuses on the definition and accuracy assessment of the reference synchrophasors in the test conditions dictated by the above IEEE Std. In the first part of the paper, we describe the characterization of a nonlinear least-squares (NL-LSQ) fitting algorithm used to determine the parameters of the reference synchrophasors. We analyse the uniqueness and robustness of the solution provided by the algorithm. We assess its accuracy within the whole range of static tests required by the IEEE Std. In the second part, we discuss the appropriateness of synchrophasor model to evaluate the PMU performance in step test conditions. We compare the proposed algorithm against two synchrophasor estimation algorithms. Finally, we propose a time domain process for the better evaluation of PMU performances in transient conditions.