It is possible to book UPS shipments with declared value if you have your own UPS agreement setup on your account.

To do this you have to add the "Declared value" service (DECLARED_VALUE), and then add the value of each package in the packages array.
For each package object you have to add a declared_value object including 2 parameters: amount and currency_code. amount is the value of the package and currency_code is the ISO-code for the currency that the value is in i.e. EUR.

The following is an example of a shipment with declared value:

{
    "own_agreement": true,
    "shipping_agent": "ups",
    "product_code": "UPS_EXPRESS",
    "service_codes": "DECLARED_VALUE",
    "sender": {
        "name": "Demo Company",
        "address1": "Strandvejen 6B",
        "zipcode": "5240",
        "city": "Odense NØ",
        "country_code": "DK",
        "email": "democompany@email.dk"
    },
    "receiver": {
        "name": "Lene Jensen",
        "address1": "Rauchstrasse 1",
        "zipcode": "10787",
        "city": "Berlin",
        "country_code": "DE",
        "email": "lene@email.de",
        "mobile": "12345678"
    },
    "parcels": [
        {
            "weight": 2315,
            "height": 24,
            "length": 37,
            "width": 23,
            "declared_value": {
                "amount": 125,
                "currency_code": "EUR"
            }
        }
    ]
}
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