The emergence of new solid-state avalanche photodetectors, e.g. SiPMs, with unprecedented timing capabilities opens new ways to profit from ultrafast and prompt photon emission in scintillators. In time of flight positron emission tomography (TOF-PET) and high energy timing detectors based on scintillators the ultimate coincidence time resolution (CTR) achievable is proportional to the square root of the scintillation rise time, decay time and the reciprocal light yield, CTR∝τrτd∕LY. Hence, the precise study of light emission in the very first tens of picoseconds is indispensable to understand time resolution limitations imposed by the scintillator. We developed a time correlated single photon counting setup having a Gaussian impulse response function (IRF) of 63ps sigma, allowing to precisely measure the scintillation rise time of various materials with 511keV excitation. In L(Y)SO:Ce we found two rise time components, the first below the resolution of our setup <10 ps and a second component being ∼380 ps. Co-doping with Ca2+ completely suppresses the slow rise component leading to a very fast initial scintillation emission with a rise time of <10ps. A very similar behavior is observed in LGSO:Ce crystals. The results are further confirmed by complementary measurements using a streak-camera system with pulsed X-ray excitation and additional 511 keV excited measurements of Mg2+ co-doped LuAG:Ce, YAG:Ce and GAGG:Ce samples.