This work proposes a methodology to estimate the statistical distribution of the probability that a 6T bit-cell starts up to a given logic value in SRAM memories for PUF applications. First, the distribution is obtained experimentally in a 65-nm CMOS device. As this distribution cannot be reproduced by electrical simulation, we explore the use of an alternative parameter defined as the distance between the origin and the separatrix in the bit-cell state space to quantify the mismatch of the cell. The resulting distribution of this parameter obtained from Monte Carlo simulations is then related to the start-up probability distribution using a two-component logistic function. The reported results show that the proposed imbalance factor is a good predictor for PUF-related reliability estimation with the advantage that can be applied at the early design stages.