You have a few issues. First you need to specify the namespace in the XPath template, the XML is not well formed (the closing tag is not the end tag), and Select-Xml returns XmlInfo, not XmlElement directly. Try the following:
$xml = [xml]@' <submission version="2.0" type="TREE" xmlns:xsi="http://www.w3.org/2001/XMLSchema-instance" xmlns:noNamespaceSchemaLocation="TREE.xsd" xmlns="some/kind/of/tree/v1"> <group> <item></item> <item></item> <item></item> </group> </submission> '@ $ns = @{dns="some/kind/of/tree/v1"} $items = Select-Xml -Xml $xml -XPath '//dns:item' -Namespace $ns $items | Foreach {$_.Node.Name}
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