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This paper presents a novel technique that allows easy and accurate estimation of the system bit error rate (BER) by collecting the statistical distribution of the receiver analog samples, i.e., before decision. It could be used to implement effective optical performance monitoring in real systems, with limited hardware complexity. The scheme performance is confirmed by both numerical simulations and experimental measurements. In all cases, the estimated BER is found to be very close to the real value, thus providing accurate and robust estimations. It is experimentally verified that in presence of strong intersymbol interference (ISI), or in the highly nonlinear regime, our technique works much better than the well known Q-factor approach.