The partitioning behaviour of carbon, phosphorous and boron during the solidification of a resistance spot weld pool was studied using experimental simulations and a phase field model. Steels with varying carbon, phosphorous and boron contents were designed and subjected to a range of resistant spot welding thermal cycles. Mechanical properties were evaluated by hardness and cross tension tests and correlated with the weld microstructure. Phase field modelling results and experimental predictions show that the phosphorus concentration in the last area in the weld pool to solidify can reach about 0.38 wt% for a steel with a bulk concentration of 0.08 wt%. Elemental analysis indicates that in the absence of boron, the grain boundaries of columnar grains in the weld pool are decorated with phosphorous. As a result, a complete interface failure occurs during cross tension testing. With the addition of boron, apart from an increase in weld strength and plug diameter, the failure mode switches to a complete plug mode, resulting from the phosphorous depletion at the grain/inter-phase boundaries.