Generally, properties such internal structure, shape, and size distribution influence the reactivity, fluidity and wettability of the crystals, and may be modified by the use of additives such as polyelectrolytes or surfactants. The aim of this study was to investigate the effect of different additives on the size and morphology of lithium carbonate crystals obtained by reactive crystallization from solutions of LiCl and Na2CO3. The additives used were: polyethylenimine (PEI), polyethylene glycol (PEG), poly (4-styrenesulfonic acid), (P4SA), polyacrylic acid (PAA), sodium dodecyl sulfate (SDS), and sodium dodecyl benzenesulfonate (SDBS). Obtained crystals were observed using scanning electron microscopy, the crystal size distribution was determined by a size image analyzer, and the crystal structure were analyzed by X-ray diffraction. The results showed that the presence of PEI, PEG and P4SA, increased the length of the lithium carbonate particles. The presence of SDS decreases the crystals size. Using SDBS as additive, the crystals had a needle-like shape, Finally PAA allowed the production of Li2CO3 spherulites. Crystal structure of lithium carbonate did not change in the presence of the tested additives.