Phase diagram of the binary system AgNO3—RbNO3 was studied using thermal analysis technique, differential scanning calorimetry and X-ray diffraction. This binary exhibits a congruently melting compound Ag0.5Rb0.5NO3 (m. p.=138°C), an incongruently melting one Ag0.33Rb0.66NO3 with two polymorphic varieties, two eutectics at (36 mol% RbNO3, 128°C) and at (60 mol% RbNO3, near 134°C) respectively and a peritectic at (60.5 mol% RbNO3, 141°C). This system contains also three invariant reactions at 164, 222 and 282°C due to the phase transitions of RbNO3 and another one at 164°C due to the phase transition of AgNO3.