摘要： Two-dimensional (2D) layered perovskites (An+1BnX3n+1, n = 1, 2, …) have lately attracted significant research interest because of their enhanced ambient stability comparing to the conventional 3D counterparts. Beside the common A-site cation engineering, using an asymmetric pseudo-halide, SCN, anion in X-site anion has been recently proven as another effective approach to constitute 2D perovskite. Among them, 2D (MA)2Pb(SCN)2I2 was most widely investigated and honored as a promising material owing to its decent optoelectronic properties; however, its poor stability arouses concerns from the recent researches. In this study, a systematical composition engineering of A2Pb(SCN)2X2 (A= FA+, MA+, Cs+ and X= Br-, I-) was conducted. Our results revealed that linear SCN- anion may dictate critical restrictions on the constituent ions of its derived 2D framework (PbX4(SCN)2), which has not been extensively discussed yet. We demonstrated that using a smaller Cs+ cation can afford a more favorable 2D structure compared with the MA+ cation. Cs2Pb(SCN)2I2 was revealed to possess improved stability and photo-response compared to (MA)2Pb(SCN)2I2. Interestingly, Cs2Pb(SCN)2I2 and (MA)2Pb(SCN)2I2 seem to possess distinct electronic band structures as indicated by their discrepant photoluminescence spectra, for which the former exhibits a rather intense singlet emission at room temperature, as opposed to the latter having a dominant emission associated with triplet or defective states. Furthermore, using a smaller Cs+ cation also enables facile replacement of smaller halide anion. A series of mix-halide 2D Cs2Pb(SCN)2(I1-xBrx)2 (x = 0, 1/3, 1/2, 2/3, 1) with variant vivid color was explored by both calculation and experimental efforts to corroborate the further enhanced stability when x value increases. The results revealed in this work might be inherent trait of 2D SCN-based perovskites and also unveil that all inorganic 2D Cs2Pb(SCN)2X2 perovskite system is a promising class of material with decent stability and color-tunability, deserving further explorations.