Potassium is deficient in most of China’s arable lands. The application of organic amendments, such as biochar, is an effective way to increase soil potassium content. The research on the interactions between long-term and annual low amount of biochar returning and potassium application on brown soil potassium, crop productivity, and soil potassium balance is not sufficient. We carried out a long-term field experiment on maize cropland, which followed a two-factor randomized block design with two factors including biochar (C) and potassium fertilizer (K). There were two levels of biochar addition (0 t·hm
-2 and 2.625 t·hm
-2; denoted as C
0 and C
1, respectively), and two potassium fertilizer levels (0 kg·hm
-2 and 60 kg·hm
-2; denoted as K
0 and K
1, respectively). Biochar and potassium fertilizer had different effects on different forms of potassium across soil layers. In 0-20 cm soil layer, the content of water-soluble potassium, slowly available potassium, available potassium, and total potassium in C
1 treatment was significantly increased by 57.14%, 17.25%, 23.48%, and 8.31% compared with C
0. On the contrary, the content of soil readily available potassium in C
1 treatment was 8.31% lower than that in C
0 treatment. The contents of soil readily available potassium, slowly available potassium, and available potassium in K
1 treatment were 16.61%, 16.42%, and 44.25% higher than those in K
0 treatment, respectively. Compared with C
0K
0 treatment, C
1K
1 significantly increased the contents of water-soluble potassium, slowly available potassium, and available potassium by 72.72%, 77.45%, and 36.19%, respectively. Biochar had a significant effect on soil water-soluble potassium content, which was contrary to that in 0-20 cm soil layer. At K
0 and K
1 levels, soil water-soluble potassium content in C
1 was significantly reduced by 8.65% and 42.57% compared with C
0, respectively. The contents of soil readily available potassium, slowly available potassium, and available potassium in K
1 treatment increased by 13.33%, 10.84%, and 19.63%, respectively, compared with K
0. The content of water-soluble potassium only in K
1 treatment decreased by 40.35% compared with K
0 at C
1 level. Compared with C
0K
0 treatment, soil water-soluble potassium content in C
1K
1 was significantly decreased by 45.51%, while available potassium content was significantly increased by 24.26%. Both biochar and potassium fertilizer could significantly increase dry weight of maize organs and total dry weight, and the potassium absorption of different organs and the whole plant. Both biochar and potassium fertilizer could significantly increase maize yield, with 8.66% higher in C
1 than in C
0, 10.10% higher in K
1 than K
0, and 19.76% higher in C
1K
1 than in C
0K
0. The application of biochar could significantly improve the absorption and utilization rate of potassium fertilizer, resulting in surplus in soil potassium. Our results indicated that the long-term return of low amount of biochar and potassium fertilizer application year by year increased potassium availability in the surface soil, improved the dry matter accumulation and potassium absorption of maize, alleviated the negative potassium balance in the soil, and enhanced maize production. The comprehensive analysis showed that the combined application of biochar and potassium fertilizer is an effective fertilization management mode to improve the effectiveness of soil potassium and increase maize yield.