Arsenic compounds, including various arsenic-containing compounds such as intravenous use of arsenic trioxide (ATO) and an oral tetra-arsenic tetra-sulfide (As4S4) -containing formula named the Realgar-Indigo naturalis formula (RIF). RIF, also known as Compound Huangdai Tablets, which exert anti-tumor effects through a variety of mechanisms, such as the induction of programmed cell death, induction of G1 or G2/M phase arrest, epigenetic regulation of miRNAs, and suppression of cancer stem cell properties. International multicenter clinical studies have shown that ATO and RIF have anti-tumorigenic effects on hematological tumors and some solids. Arsenic compounds also been used in the treatment of cervical cancer, endometrial cancer, ovarian cancer, especially advanced drug-resistant ovarian cancer. This article introduces the progress of ATO in combination chemotherapy, such as ATO with paclitaxel, adriamycin, cisplatin, etc in solid tumors and gynecological malignant tumors. The side effects associated with arsenic treatment, including cardiac disorders, skin and bone marrow suppression, etc. are also discussed in this review. Oral arsenic drugs also have a good therapeutic effect, it may be an outpatient oral chemotherapy new model for RIF to treatment recurrent ovarian cancer.