A template‐agent can affect defect formation as well as influence interface properties, due to the rapid growth of perovskite film from the solution. Herein, diethylammonium iodide (DAI) is used as an effective template‐agent to control the perovskite crystallization during preparation. It is found that a very small amount of DAI in chlorobenzene (CB) can slow down the perovskite growth of the CH3NH3PbI3 (MAPbI3) film with more large grain size and compacted crystal‐grains resulting in the lesser grain boundaries (GBs) in favor of carrier transport in perovskite solar cells (PSCs). Moreover, some redundant PbI2 can be digested to form DA2PbI4. One part of DA2PbI4 can form the sub‐grains with the composition of (DA2PbI4)0.2(PbI2)0.8 to passivate the GB defects, and other part can cover the surface to passivate the surface defects in large MAPbI3 grains. Using an optimized DAI concentration of 0.5 mg mL−1 in CB solution, the corrsponding MAPbI3 PSC achieves an increased power conversion efficiency of 20.31% with suppressed current–voltage hysteresis. This DAI passivation strategy provides a simple approach to effectively assist the grain‐growth for improved device performance.