MnO doped calcium fluoroborophosphate glasses of the composition 20 CaF2–50 P2O5–(30−x)B2O3:x MnO in mol% with x ranging from 0.2 to 1.0 (in steps of 0.2) were synthesized. The samples were exposed to different γ-ray doses in the range 250–1000Gy and their thermoluminescence (TL) was recorded in the temperature range ambient to 300°C. The glow curves of all these samples exhibited an intense principal peak at about 200°C followed by a feeble high temperature peak at about 300°C. The TL response of integral TL output as well as TL of the principal peak exhibited perfectly linear increase with the dose within the range of 250–1000Gy. However, the gradual increase of MnO content in the glass matrix caused a decrement in the TL output. Such mechanism is explained based on different valence states of Mn ions in the glass matrix and the quenching effect is assumed to be well exploited to measure the high radiation doses required in radiation processing facilities without saturating the PMT of the reader. The comparison of TL response of the studied glasses with that of CaSO4:Dy phosphor indicated an improvement in the dose response in terms of linearity and adequate sensitivity for the measurement of high doses.