Artificial potassium silicate fertilizer (PSF) is a typical slow-release potassium fertilizer. However, the exact minerals that are released by PSF and the nutrients that are made available to plants remain unclear. This study quantitatively investigated the behaviour of nutrients released from PSF by the batch-release test and their supply to plants by the plant growth tests, respectively, to determine the quantitative relationship between nutrients released from PSF and taken up by the plant. X-ray diffraction (XRD) analysis showed that kalsilite, åkermanite, and potassium–magnesium silicate were the most abundant crystalline minerals in PSF. The XRD peaks of åkermanite and potassium–magnesium silicate were absent after citric acid extraction at a liquid/solid ratio of 20 to 100 (CA20 and CA100). Magnesium-use efficiencies in PSF (11%) and residue treatments after ammonium acetate extraction (AC, 10%) were higher than those in residue treatments after CA20 (1.8%) and CA100 (6.0%). Potassium (%) released by AC in the batch-release test (4.5%) was compatible with the difference of potassium-use efficiencies between the treatments of PSF (21%) and the AC-residue (16%). Likewise, potassium (%) released by CA20 (8.8%) was lower than the difference of potassium-use efficiencies between the treatments of PSF (21%) and CA20-residue (7.9%). This study suggests that potassium is rapidly released from potassium–magnesium silicate in PSF and is readily available to plants.