Flexible aliphatic poly(lactic acid) is introduced into polyethylene terephthalate through copolymerization to prepare biodegradable copolyester, which aims to solve the non-degradability of polyethylene terephthalate (PET) and realize the greening of raw materials. In this work, poly(ethylene terephthalate-co-lactic acid) random copolyesters (PETLAs) of lactic acid composition from 10 to 50% is synthesized via one-pot method. The chemical structure and composition, thermal property, and crystallization property of prepared PETLAs resin are characterized. The results shows that the introduction of LA segment forms random copolyester, and the flexible LA segment results in slight decrease in the glass transition temperatures (Tg ), melting point (Tm ), and crystallinity (Xc ) of the copolyesters. The thermal stability of PETLAs is better, and the initial decomposition temperature of PETLA-10 can reach 394 °C. The PETLAs resin exhibits good processability, and PETLAs fibers are prepared by melt spinning. The strength of PETLA-10 fiber can reach 260 MPa after drawing treatment, and the elongation at break can reach 130%. Taking advantage of their features, PETLAs as an innovative bio-based polymer are expected to achieve ecofriendly applications in the fields of fiber, plastic, and film.