In the paper results of single- and double-pulse LIBS (Laser-Induced Breakdown Spectroscopy) measurements in collinear geometry are described. The experiments were performed using a unique self-made Nd:YAG laser operating in the Q-switching regime, where the laser transmission losses are switched. Such a laser allowed for an easy and quick change of the operating mode (one and two pulses), free shaping of the energy ratio of the two pulses (division of the energy of a single pulse into two parts) and a smooth change of the delay time between pulses in the range from 200 ns to 10 μs. To our knowledge, such a laser was used in LIBS measurements for the first time. LIBS experiments revealed strong self-absorption depending on energy ratios carried out in the first and second laser pulse in the double-pulse mode. This was confirmed also by statistical factorial analysis of LIBS spectra. Plasma temperature and LIBS signal enhancement were measured both for energy proportions between the first and the second laser pulse and for the first-to-second-pulse delay.