Synthesizing polymers with tailor-made molecular weight distribution (MWD) is an essential step toward better control and design of functional polymer materials. We propose a novel one-pot reaction strategy that can facilitate the inverse design of the shape, breadth, and skew of the MWD in a controlled polymerization. By a multistep initiator addition scheme that involves a sequence of addition operations with determined amounts of initiators and addition times, the polymers with target MWD can be possibly synthesized. This strategy is in principle suitable to reproduce most target MWDs, even with a multimodal profile or with large breadth and/or skew. As compared to previous relevant methods by blending polymers with determined molar masses and ratios, this one-pot reaction strategy avoids most of the tedious intermediate steps for controlling precision in blending and would be more convenient and timesaving. Our study supplies the inspiration of better control of synthesizing polymers with designated MIND in controlled polymerization.