Bulk (GeTe₄)_100 − x(As₂Se₃)_x(0 ≤ x ≤ 60) glasses in the tie-line GeTe₄-As₂Se₃prepared by melt quenching method are characterized by differential scanning calorimetry (DSC), X-ray diffraction and Raman spectroscopy. In covalent network glasses, the structural network transform from a floppy to a rigid structure at an average coordination number (Z_av) 2.40. (GeTe₄)_100 − x(As₂Se₃)_x glasses in the range 5 ≤ x ≤ 15 exhibit two stage crystallization whereas glasses with x > 15 exhibit single stage crystallization. Annealing of the glasses results into hexagonal GeTe and Te structures for 0 ≤ x ≤ 10 whereas glasses in the range 15 ≤ x ≤ 40 show only Te crystallites. For higher As₂Se₃ mol. % (x ≥ 50) As₂Te₃ phase along with Te has been observed. Raman studies indicate the presence of GeSe₂, GeTe₂, As₂Te₃, and -Te-Te-structural units. The average coordination number of the glasses prepared in this tie-line is 2.4. Though the overall bond energy of the system increases with the increase of As₂Se₃, the density (ρ), glass transition (T_g) and specific heat capacity (∆ C_p) show a decreasing trend. The rate of decrease of ρ, T_g and ∆ C_p is slow for 0 ≤ x < 25 and rapid for 25 ≤ x ≤ 40. These results indicate that the rigidity of the structural network decreases with an increase of As₂Se₃ though the average coordination number remains constant for the entire range of composition.