NaCl crystal nucleation from metastable solutions has long been considered to occur according to a single-step mechanism where the growth in the size and crystalline order of the emerging nuclei is simultaneous. Recent experimental observations suggest that significant ion–ion correlations occur in solution and that NaCl crystals can emerge from disordered intermediates which is seemingly at odds with this established view. Here, we performed biased and unbiased molecular dynamics simulations to analyse and characterise the pathways to crystalline phases from solutions far into the metastable region. We find that large liquid-like NaCl clusters emerge as the solution concentration is increased and a wide distribution of crystallisation pathways are observed with two-step nucleation pathways—where crystalline order emerges in dense liquid NaCl regions—being more dominant than one-step pathways to phase separation far into the metastable region. Analyses of cluster size populations and the ion pair association constant show that these clusters are transient, unlike the thermodynamically stable prenucleation cluster solute species that were suggested in other mineralising systems. A Markov state model was developed to analyse the mechanisms and timescales for nucleation from unbiased molecular dynamics trajectories in a reaction coordinate space characterising the dense regions in clusters and crystalline order. This allowed calculation of the committor probabilities for the system to relax to the solution or crystal states and to estimate the rate of nucleation, which shows excellent agreement with literature values. From a fundamental nucleation perspective, our work highlights the need to extend the attribute ‘critical’ to an ensemble of clusters which can display a broad range of structures and include sizeable disordered domains depending upon the reaction conditions. Moreover, our recent simulation studies demonstrated that carbon surfaces catalyse the formation of liquid-like NaCl networks which, combined with the observations here, suggests that alternative pathways beyond the single-step mechanism can be exploited to control the crystallisation of NaCl.