The growth and degradation of poly(glycolic acid) (PGA) and poly(epsilon-caprolactone) (PCL) brushes were compared. Using tin (octanoate) as the catalyst, optimal conditions were found for growth of each polyester brush from the hydroxy-terminated silicon surface via ring-opening polymerization. PCL brushes grew thicker at elevated temperatures but the thickest PGA brushes grew at room temperature. Unlike bulk polyesters that can degrade under both acidic and basic conditions, the confined surface polyester brushes only degraded under neutral or basic conditions. The degradation mechanism of grafted polyester brushes was probed through a blocking test. It was shown that the terminal hydroxy groups of these polyester brushes were essential to the degradation process indicating a preferential backbiting mechanism. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4643-4649