The microbial production of platform chemicals like 5-aminovaleric acid (5AVA) and putrescine presents a green alternative to petroleum-based synthesis, particularly for bio-based polyamides and pharmaceutical precursors. In this study, we employed metabolically engineered Corynebacterium glutamicum strains (AVA Xyl and PUT Xyl) for efficient biosynthesis of 5AVA and putrescine in CGXII minimal medium. Initial medium optimization through one-factor-at-a-time (OFAT) experiments identified key components glucose, ammonium sulphate, MOPS, and urea, yielding 4.1 ± 0.21 g per L 5AVA and 0.41 ± 0.01 g per L putrescine. Through successive sub-culturing of PUT Xyl and fermentation, the putrescine titer was improved to 1.82 ± 0.39 g L⁻¹. Further statistical optimization using central composite design (CCD) significantly enhanced the production, achieving 6.0 ± 0.54 g L⁻¹ of 5AVA and 6.44 ± 0.33 g L⁻¹ of putrescine. Putrescine was concentrated up to 14.3 ± 0.6 g L⁻¹ via controlled evaporation, and 5AVA was recovered using Dowex 50W-X8 resin in ion exchange chromatography with 84 ± 2% yield. The process design minimized the use of toxic reagents and leveraged water-based, low-energy downstream methods. The integrated approach demonstrates a scalable, environmentally benign route to high value monomers, through green processing strategies.