Benzyl 1-O-acyl-2,3,4-tri-O-benzyl-D-glucopyranuronates were synthesised by different routes and catalytically debenzylated into 1-O-acyl-D-glucopyranuronic acids. Both anomers of 1-O-benzoyl-, 1-O-p-methoxybenzoyl-, and 1-O-3′,4′-dimethoxybenzoyl-D-glucopyranuronic acids were obtained; they represent the first known anomeric pairs in this series. Some 1-O-acyl glucuronic acids were converted into their methyl 2,3,4-tri-O-acetyl derivatives.