Experimental results are presented here obtained by a drop calorimetric method, in which Ni and Cu particles, both in bulk and nanosized form, were dropped into a liquid Sn-3.8Ag-0.7Cu solder alloy (in wt%). The molar enthalpies of mixing of the liquid (Sn-3.8Ag-0.7Cu)–Ni(Cu) alloys were measured. An extra exothermic heat effect is observed when dropping nano-particles instead of macro-particles. This is partly due to the loss of the large surface area and the corresponding large surface enthalpy of the nano-particles before their dissolution in the liquid alloy. However, a large additional exothermic heat effect was also found in the case of Cu-nano-particles, due to the exchange chemical reaction between the Cu2O shell of the nano-particles and liquid Sn; this is caused by the fact that the Cu-nano-particles are core–shell particles with an inner metallic Cu core and an outer Cu2O shell. This effect is less significant for Ni nano-particles which have a thinner oxide shell.