How can I format a decimal bound to TextBox without angering my users?

Try to resolve that on ViewModel level. That it:

public class FormattedDecimalViewModel : INotifyPropertyChanged
    {
        private readonly string _format;

        public FormattedDecimalViewModel()
            : this("F2")
        {

        }

        public FormattedDecimalViewModel(string format)
        {
            _format = format;
        }

        private string _someDecimalAsString;
        // String value that will be displayed on the view.
        // Bind this property to your control
        public string SomeDecimalAsString
        {
            get
            {
                return _someDecimalAsString;
            }
            set
            {
                _someDecimalAsString = value;
                RaisePropertyChanged("SomeDecimalAsString");
                RaisePropertyChanged("SomeDecimal");
            }
        }

        // Converts user input to decimal or initializes view model
        public decimal SomeDecimal
        {
            get
            {
                return decimal.Parse(_someDecimalAsString);
            }
            set
            {
                SomeDecimalAsString = value.ToString(_format);
            }
        }

        // Applies format forcibly
        public void ApplyFormat()
        {
            SomeDecimalAsString = SomeDecimal.ToString(_format);
        }

        public event PropertyChangedEventHandler PropertyChanged;

        private void RaisePropertyChanged(string propertyName)
        {
            if (PropertyChanged != null)
                PropertyChanged(this, new PropertyChangedEventArgs(propertyName));
        }
    }

SAMPLE

Xaml:

<TextBox x:Name="tb" Text="{Binding Path=SomeDecimalAsString, UpdateSourceTrigger=PropertyChanged}" />

Code behind:

public MainWindow()
{
    InitializeComponent();
    FormattedDecimalViewModel formattedDecimalViewModel = new FormattedDecimalViewModel { SomeDecimal = (decimal)2.50 };
    tb.LostFocus += (s, e) => formattedDecimalViewModel.ApplyFormat(); // when user finishes to type, will apply formatting
    DataContext = formattedDecimalViewModel;
}