Chilean volcanic soils contain large amounts of total and organic phosphorus, but P availability is low. Phosphobacteria [phytate-mineralizing bacteria (PMB) and phosphate-solubilizing bacteria (PSB)] were isolated from the rhizosphere of perennial ryegrass (Lolium perenne), white clover (Trifolium repens), wheat (Triticum aestivum), oat (Avena sativa), and yellow lupin (Lupinus luteus) growing in volcanic soil. Six phosphobacteria were selected, based on their capacity to utilize both Na-phytate and Ca-phosphate on agar media (denoted as PMPSB), and characterized. The capacity of selected PMPSB to release inorganic P (Pi) from Na-phytate in broth was also assayed. The results showed that from 300 colonies randomly chosen on Luria–Bertani agar, phosphobacteria represented from 44% to 54% in perennial ryegrass, white clover, oat, and wheat rhizospheres. In contrast, phosphobacteria represented only 17% of colonies chosen from yellow lupin rhizosphere. This study also revealed that pasture plants (perennial ryegrass and white clover) have predominantly PMB in their rhizosphere, whereas PSB dominated in the rhizosphere of crops (oat and wheat). Selected PMPSB were genetically characterized as Pseudomonas, Enterobacter, and Pantoea; all showed the production of phosphoric hydrolases (alkaline phosphatase, acid phosphatase, and naphthol phosphohydrolase). Assays with PMPSB resulted in a higher Pi liberation compared with uninoculated controls and revealed also that the addition of glucose influenced the Pi-liberation capacity of some of the PMPSB assayed.