Complimentary optical diagnostic tools are applied to provide comprehensive analysis of thermal phenomena in millisecond Nd:YAG laser irradiation of steel substrates. The following optical devices are employed: (a) infrared camera FLIR Phoenix RDASTM equipped by InSb sensor with 3 to 5 µm band pass arranged on 320 × 256 pixels array, (b) ultra-rapid camera Phantom V7.1 with SR-CMOS monochrome sensor in the visible spectral range, up to 105 frames per second for 64 × 88 pixels array, (c) original multi-wavelength pyrometer in the near-infrared range (1.370–1.531 µm). The following laser radiation parameters are applied: variation of energy per pulse in the range 15–30 J at a constant pulse duration of 10 ms with and without application of protective gas (Ar). The evolution of true temperature is restored based on the method of multi-colour pyrometry; by this way, melting/solidification dynamics is analysed. Emissivity variation with temperature is studied, and hysteresis type functional dependence is found. Variation of intensity of surface evaporation visualised by the camera Phantom V7.1 is registered and linked with the surface temperature evolution, different surface roughness and influence of protective gas atmosphere. Determination of the vapour plume temperature based on relatively intensities of spectral lines is done. The numerical simulation is carried out applying the thermal model with phase transitions taken into account.