The coincidence timing resolution is a critical parameter which to a large extent determines the system performance of positron emission tomography (PET). This is particularly true for time-of-flight (TOF) PET that requires an excellent coincidence timing resolution (<<1 ns) in order to significantly improve the image quality. The intrinsic timing resolution is conventionally calculated with a single-exponential timing model that includes two parameters of a scintillator detector: scintillation decay time and total photoelectron yield from the photon-electron conversion. However, this calculation has led to significant errors when the coincidence timing resolution reaches 1 ns or less. In this paper, a bi-exponential timing model is derived and evaluated. The new timing model includes an additional parameter of a scintillator detector: scintillation rise time. The effect of rise time on the timing resolution has been investigated analytically, and the results reveal that the rise time can significantly change the timing resolution of fast scintillators that have short decay time constants. Compared with measured data, the calculations have shown that the new timing model significantly improves the accuracy in the calculation of timing resolutions.