The use of low molecular weight organic acids (LMWOAs) for the phytoremediation of heavy metals has become a promising technique. We chose five kinds of organic acids (oxalic acid (OA), acetic acid (AA), tartaric acid (TA), malic acid (MA), and citric acid (CA)) with six application rates (1, 2, 3, 4, 5, and 6 mmol/kg) and planted sunflowers (Helianthus annuus L.) in Cd-polluted soil to study the efficiency of the phytoremediation of Cd and the degree of Cd toxicity to plants. Treatment with no acid application served as the control (CK). We analyzed the plant height dry matter and the Cd and nonprotein sulfhydryl (NPT) contents in the soil and plant tissues. OA, AA, TA, MA, and CA increased plant heights by 17.6–47.40%, 21.25–39.17%, 12.5–35.52, 5.10–30.50%, and 16.15–49.17%, respectively; shoot biomass of the sunflowers was increased except with MA. NPT decreased under LMWOA application, which, in the roots, increased with the increase in root Cd under LMWOA treatment; however, there was no obvious relationship in the stems and leaves. The composition of Cd in the soil changed significantly under the LMWOA treatments compared to the CK, and the changes in carbonate Cd and Fe-Mn oxide Cd were the most prominent. The plant Cd accumulation of OA, AA, TA, MA, and CA increased by 43.31%, 55.25%, 48.69%, 0.52%, and 32.94%, respectively, and the increase in root Cd content and shoot dry matter quality promoted the increase in Cd accumulation. The LMWOAs were more likely to affect the phytoremediation of Cd by changing total P (TP) rather than total N (TN).