Magnesium phosphate glasses exhibit unusual properties and were classified as 'anomalous phosphate glasses', because magnesium is attributed to a variation of the oxygen coordination number from 6 to 4. Magnesium in phosphate glasses acts as an intermediate oxide and its role was determined, relating to the phosphate chain length. In the present work, MgOP 2 O 5 TiO 2 / Nb 2 O 5 glasses with Mg/P ratio between 1.00 and 1.36 were successfully prepared by a meltquenching method. Magnesium in the glasses worked as a network former to form POMg bonds, which are cross-linked short phosphate chains that improved the glass-forming ability. Intermediate oxides (i.e., TiO 2 and Nb 2 O 5 ) in the glasses also cross-linked short phosphate chains to form P OTi/Nb bonds. The chemical durability of the glasses decreased with an increase in the Mg/P ratio, because magnesium, which entered the phosphate network, weakened the glass network to induce hydrolysis. The dissolution rate of Ti 4+ and Nb 5+ ions showed a decreasing tendency with an increase in the Mg/P ratio. The surfaces of the glasses were considered to be covered with gel-like oxide layers containing titanium or niobium and phosphate.