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Код

            DataGridViewComboBoxColumn comboBox = new DataGridViewComboBoxColumn();
            DataTable comboTable = new DataTable();
            DataColumn column = new DataColumn();
            column.DataType = typeof(int);
            column.ColumnName = "Col1";
            comboTable.Columns.Add(column);
            column = new DataColumn();
            column.DataType = typeof(string);
            column.ColumnName = "Col2";
            comboTable.Columns.Add(column);
            comboTable.Rows.Add(new object[] { 1, "R" });
            comboTable.Rows.Add(new object[] { 2, "Y" });
            comboTable.Rows.Add(new object[] { 3, "B" });
            comboBox.DataSource = comboTable;
            comboBox.DisplayMember = "Col2";
            comboBox.ValueMember = "Col1";