Developing promoters that can boost the growth quality, efficiency, and robustness of two-dimensional (2D) transition metal dichalcogenides is significant for their industrial applications. Herein a new group (group IIA) of promoters in the periodic table has been disclosed, whose chlorides (especially CaCl2 and SrCl2) exhibit a versatile promoting effect on the CVD growth of various TMD monolayers, including hexagonal MoS2, MoSe2, Re doped MoS2, and triclinic ReS2. The promoting effect of group IIA promoters relies on the appropriate dose and is strongly substrate-dependent. The performances of five typical group IA-IIA metal chlorides are ranked by quantitative investigations, displaying periodic variations closely related to the electronegativities of the metal elements. A brand-new acid-base match model is proposed, attributing the promoting mechanism to an increase of the substrate basicity due to the usage of promoters, thus leading to the sufficient adsorption of the acidic precursor. Aberration-corrected annular dark field scanning transmission electron microscopy (ADF-STEM) was applied, unveiling anomalous grain boundaries (GBs) with a low density of coincident sites in the as-grown ReS2 and detailed atomic configurations of Re doped MoS2. This work expands the promoter library and gives an insight into GB engineering for the CVD growth of 2D TMDs.