Poly(pentylene glycol azelate) (PPeAz), an odd-odd aliphatic polyester, was synthesised by solution polycondensation using n-butyl titanate, isopropyl titanate, tin isooctanoate, anhydrous stannous chloride, and p-benzene methanesulfonic acid as catalysts, respectively. The effects of different catalytic systems on the characteristic viscosity, chemical structure, crystal structure, thermal properties and enzymatic properties of PPeAz were investigated. The relative viscosities of PPeAz prepared with different catalysts were in the following order: Titanium tetraisopropanolate > Tetrabutyl titanate > P-toluenesulfonic acid > Stannous octoate > Tin(II) chloride > Catalyst-free. The white PPeAz catalyzed by isopropyl titanate had the shortest polycondensation time of only 6 h, the highest yield, the largest characteristic viscosity of 0.857 dL/g, the lowest crystallinity, the highest melting temperature, the best thermal stability, the fastest enzyme degradation rate, and the degradation could be completed in 12 h. The relative viscosities of PPeAz were as follows.