The capital city of Estado Bolívar is homonymous Ciudad Bolívar, but the largest city is Ciudad Guayana. It is bordered to the north by the Orinoco River and to the south by the Federative Republic of Brazil. To the east is the territory of Guayana Esequiba, which is currently controlled by Guyana. However, Venezuela claims to be the actual owner of the territory, which caused Guyana–Venezuela territorial dispute, and the 2023 Guayana Esequiba crisis.
The state has three major landscapes, the Orinoco savannahs and low mountains, the area of the table mountains called tepuis, and the lowlands of the Yuruari. The basic geologic formation is an old craton, named the Guiana shield, with very old rocks of Precambrian origin. The tepuis are located in an area which is normally between 300 m and 500 m asl and numerous rivers drain the area. The top of the table mountains is between 1,700 m and 2,000 m asl.