Grease an 8 cup-capacity metal pudding steamer. Line base with baking paper.
Using an electric mixer beat butter, sugar and orange rind until light and fluffy. Add eggs, 1 at a time, beating to combine. Sift flour over mixture. Add milk. Fold until just combined.
Spoon mixture into prepared steamer. Smooth top. Secure lid. Place in a large saucepan. Carefully pour boiling water into pan until halfway up side of steamer. Cover pan. Place over medium heat. Bring to the boil. Reduce heat to low. Simmer for 1 hour 30 minutes, topping up with boiling water when necessary.
Meanwhile, make syrup Combine orange juice and sugar in a saucepan over medium heat. Cook, stirring for 3 minutes or until sugar dissolves (do not boil). Bring to the boil. Reduce heat to low. Simmer for 5 minutes or until thick and syrupy. Remove from heat. Add orange segments.
Remove pan from heat. Carefully lift steamer from water. Stand for 10 minutes. Remove lid. Turn pudding onto a plate. Spoon over syrup. Serve.