Undoped Ca3Al2O6 phosphor was successfully synthesized through a gel-combustion method using different fuels. It was characterized by X-ray diffraction (XRD) technique and its cubic phase structure was confirmed from XRD pattern. TL data were recorded from room temperature (RT) to 500 °C in the heating rate of 2 °C/s. The glow curves of Ca3Al2O6 sample exposed to different beta doses (0–200 Gy) exhibited a significant glow peak at about 184 °C. The TL intensity of the glow peak exhibited very good linearity between 0.1 and 10 Gy. Following this, it was decreased at higher doses which was referred to this effect as monotonic dose dependence. Initial rise (IR), peak shape (PS), and variable heating rate (VHR) methods were used to estimate trapping parameters. Computerized glow curve deconvolution (CGCD) method via TLAnal software was also applied to estimate the number of peaks and kinetic parameters corresponding to the main glow curve in Ca3Al2O6 sample. The trapping activation energy of the main dosimetric peak was calculated to be around 1.30 eV for all methods. Present findings confirm that Ca3Al2O6 host is a promising candidate for applications in environmental dosimetry as one depicts good TL dose response with adequate sensitivity and linearity.