Phase and morphology evolution of PCC precipitated during carbonation of calcium-rich solution with/without additives. Display omitted •Rhombohedral calcite switched to spherical vaterite during the gas–liquid carbonation process.•Organic additives delay or change the phase transition pathway of PCC.•Pure spherical vaterite can be produced in the CO2 mineralization process.•Organic additives may influence the growth morphology by coordinating with a specific crystal plane of PCC. The indirect CO2 mineralization by using Ca/Mg-containing industrial alkaline by-products or wastes is a promising way for mitigation of CO2 emissions and valorization of wastes, although plagued by the utilization of precipitated calcium carbonate (PCC) if low-value product is obtained. It is difficult to acquire specific PCC with targeted morphology for commercial use since many parameters change in the gas–liquid carbonation process. In this work, the phase transition and morphology evolution behavior of PCC precipitated during carbonation of 0.1 mol·L−1 NH4Cl Ca-rich solution were studied. Results show that the polymorph transformation from rhombohedral calcite to spherical vaterite was found during the gas–liquid carbonation process, which is different from the traditional carbonation process (aqueous carbonation of lime). A promising result is that pure spherical vaterite of industrial interest was obtained under the studied conditions. In addition, to achieve conversion of CO2(g) into desired morphology of PCC, the feasibility of introducing additives (ethylene glycol and citric acid) into the gas–liquid carbonation system was also evaluated in terms of CO2(g) adsorption and PCC polymorphs control. Finally, the mechanism of additives on the growth and morphology of crystalline CaCO3 was investigated by FTIR and interpreted at the atomic level.