We have studied the calibration of PMTs in scintillation detectors, inducing single electron response on the PMT from primary scintillation produced by x-ray interaction. The results agree with those obtained by the commonly used single electron response (SER) method, which uses LED light pulses to induce the PMT SER. The use of the primary scintillation for PMT calibration will be convenient in situations where the PMT is already in situ, when it becomes difficult or even impossible to apply the SER method, e.g. in commercial sealed scintillator/PMT devices. Furthermore, we have experimentally investigated the possibility of fitting the high-charge tail of the PMT SER pulse-height distribution to an exponential function, inferring the PMT gain from the inverse of the exponent. The results of the exponential fit method agree with those obtained by the SER method for pulse-height distributions resulting from an average number of around 1.0 photoelectrons reaching the first dynode per light/scintillation pulse. The SER method has higher precision and, therefore, is used in a larger number of applications. Nevertheless, the exponential fit method will be useful in situations where the single photoelectron peak is under the background or noise peak and it may present an alternative, simple way, for relative gain calibration of PMT arrays as well as for monitoring the PMT gain variations.