We report on a Laser Induced Breakdown Spectroscopy (LIBS) system with a very high temporal resolution, using femtosecond and picosecond pulse laser excitation of pure aluminum (Al). By using a 140 fs Ti:Sapphire laser in an ultrafast optical Kerr gate (OKG), we demonstrate LIBS sampling with a sub-ps time resolution (0.8 ± 0.08 ps) in a 14 ns window. The width of the gating window in this system was as narrow as 0.8 ps, owing to the inclusion of a carbon disulfide (CS2) cell, which has a fast response and a large nonlinear coefficient. Furthermore, when using a 100 ps pulsed Nd:YAG laser and a fast photomultiplier tube (PMT) we demonstrate a LIBS system with a nanosecond time resolution (2.20 ± 0.08 ns) in a microsecond window. With this sort of temporal resolution, a noncontinuous decay in the Al signal could be observed. After 50 ns decay of the first peak, the second peak at 230 ns is started to perform. Experimental results with such short temporal windows in LIBS, in both nanosecond and microsecond ranges, are important for fast temporal evolution measurements and observations of early continuum emission in materials.