Disclosed is a process for manufacturing underground caverns suitable in one embodiment for storage of large volumes of gaseous or liquid materials. The method is an acid dissolution process that can be utilized to form caverns in carbonate rock formations. The caverns can be used to store large quantities of materials near transportation facilities or destination markets. The caverns can be used for storage of materials including fossil fuels, such as natural gas, refined products formed from fossil fuels, or waste materials, such as hazardous waste materials. The caverns can also be utilized for applications involving human access such as recreation or research. The method can also be utilized to form calcium chloride as a by-product of the cavern formation process.