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Is there anything to look out for when buying an older model Holden Combo van with high kms?

Obviously, any older high mileage vehicle can pose a risk, so it would pay to check it over thoroughly, particularly if this vehicle has been used for commercial purposes, as basically it is just a car (based on the Barina), so not a really robust commercial.
Engine, gearbox, clutch, suspension components etc may all be subject to wear on a high mileage vehicle. Check on the service history and make sure it has been regularly serviced - and check that the cambelt is within servicable limits. Check the coolant and make sure it is a nice green colour and not rusty looking. Also, check to see when the brake fluid was last changed. Obvious things such as tyre condition, evidence of body repairs, corrosion and cosmetic defects etc should be checked too.
Ultimately, if you're not sure, have the vehicle professionally inspected.