To achieve efficient doping in polymer solar cells (PSCs), the dopant needs to be selectively located in the binary components of a bulk heterojunction (BHJ) film according to its polarity. The rarely studied n-type dopant is thoroughly examined in a simplified planar heterojunction (PHJ) device to address its favored location in the active layer. Results show that the n-dopant distribution in the acceptor layer or at the donor/acceptor interface produces enhanced device performance, whereas it harms the device when located in the donor layer. Based on the results, the benefit of n-type doping is then transferred to the highly efficient BHJ devices via a sequential coating procedure. The performance improvement is closely linked to the variations in the dopant's location in the BHJ film, which is carefully examined by the synchrotron techniques with delicate chemical sensitivity. More interestingly, the sequential coating procedure can be easily extended to the p-doped device only by changing the dopant's polarity in the middle layer. These findings pave the way for ambipolar doping in PSCs and enable performance improvement by molecular doping within the expectations.