Witherite originates from the biochemical sedimentation of barium in sea water. Due to the complexity of the metallogenic environment, witherite appears in many morphologies. However, the relationship between its diverse morphologies and its mineralisation environment is not well understood. In this paper, Ca2+, a common substitute for Ba2+, and mixed protein (egg white) were used to simulate the inorganic and organic environments of witherite mineralisation, respectively. Comparison of samples prepared under different conditions showed that Ca2+ and egg white have relatively independent regulatory effects on the mineralisation of witherite particles. Egg white primarily limits the growth of the nanocrystals, while Ca2+ directs their non-isodiametric growth. Results shows that Ca2+ is distributed along a gradient in nanocrystalline witherite particles, with the Ca2+ content being proportional to the diameter of the nanocrystals. The results of this study shed light on the different roles of organic matter and inorganic ions in the formation of witherite and offer insight into the genesis of its various morphologies.