Electrochemical carbon dioxide reduction reaction (CO2RR) is an environmentally friendly and economically viable approach to convert greenhouse gas CO2 into valuable chemical fuels and feedstocks. Among various products of CO2RR, formic acid/formate (HCOOH/HCOO−) is considered the most attractive one with its high energy density and ease of storage, thereby enabling widespread commercial applications in chemical, medicine, and energy‐related industries. Nowadays, the development of efficient and financially feasible electrocatalysts with excellent selectivity and activity towards HCOOH/HCOO− is paramount for the industrial application of CO2RR technology, in which Tin (Sn), Bismuth (Bi), and Indium (In)‐based electrocatalysts have drawn significant attention due to their high efficiency and various regulation strategies have been explored to design diverse advanced electrocatalysts. Herein, we comprehensively review the rational strategies to enhance electrocatalytic performances of these electrocatalysts for CO2RR to HCOOH/HCOO−. Specifically, the internal mechanism between the physicochemical properties of engineering materials and electrocatalytic performance is analyzed and discussed in details. Besides, the current challenges and future opportunities are proposed to provide inspiration for the development of more efficient electrocatalysts in this field.