Fluorophosphate glasses with various Al(PO3)3 content were prepared, and their structure, thermal properties and spectral properties were studied. For these glasses, with the increment of Al(PO3)3 content, the density decreased while the refractive index increases, and transition temperature, the onset and maximum of the crystallization peak temperature and melt temperature increased which were suggested by differential scanning calorimetry. These glasses exhibited the best resistance against crystallization with 7%～9% mole concentration Al(PO3)3 content. Normalized Raman spectrums were used to analyze structure and phonon status. For these glasses the increment of Al(PO3)3 content did not affect phonon energy but resulted in the augment of phonon density. Absorption spectrums were measured. 3H6→3F4 exhibited absorption at L band of the third communication window. Compared with the Tm3+ excited states in other glass system, 3F4 energy level of Tm3+ in these glasses was slightly higher and 3H4 energy level was slightly lower, so it could be predicted that emission band of 3H4→3F4 transition was similar to the amplified band of the gain-shift Tm3+ doped fiber amplifier with a relatively long wavelength. Analyses with Judd-Ofelt theory suggested with the increment of Al(PO3)3 content, phenomenological intensity parameter Ω2 increased, Ω6 varied little, and the radiative lifetime of Tm3+ excited states decreased.