To create a multiple custom options of a product in single time you can use below piece of code
<?php
require_once 'app/Mage.php';
Mage::app();
$productId = 905; // your product id
$product = Mage::getModel('catalog/product')->load($productId);
$options = array(
array(
'title' => 'Color',
'type' => 'drop_down',
'is_required' => 1,
'sort_order' => 0,
'values' => array(
array(
'title' => 'Red',
'price' => 10.50,
'price_type' => 'fixed',
'sku' => '',
'sort_order' => 0,
),
array(
'title' => 'Gold',
'price' => 0,
'price_type' => 'fixed',
'sku' => '',
'sort_order' => 0,
)
)
),
array('title' => 'size',
'type' => 'drop_down',
'is_required' => 1,
'sort_order' => 0,
'values' => array(
array(
'title' => 'small',
'price' => 10.50,
'price_type' => 'fixed',
'sku' => '',
'sort_order' => 0,
),
array(
'title' => 'large',
'price' => 0,
'price_type' => 'fixed',
'sku' => '',
'sort_order' => 0,
)
)
)
);
//print_r($options);die;
foreach($options as $options1){
$product->getOptionInstance()->unsetOptions();
$optionsnew = array($options1);
$product->setProductOptions($optionsnew);
$product->setCanSaveCustomOptions(true);
$product->save();
}
?>