diff --git a/Lib9c/Action/InvalidItemIdException.cs b/Lib9c/Action/InvalidItemIdException.cs
new file mode 100644
index 0000000000..ca1e7c0b29
--- /dev/null
+++ b/Lib9c/Action/InvalidItemIdException.cs
@@ -0,0 +1,36 @@
+using System;
+using System.Runtime.Serialization;
+
+namespace Nekoyume.Action
+{
+    /// <summary>
+    /// Represents an exception that is thrown when an invalid item ID is used.
+    /// </summary>
+    [Serializable]
+    public class InvalidItemIdException : ArgumentOutOfRangeException
+    {
+        /// <summary>
+        /// Initializes a new instance of the <see cref="InvalidItemIdException"/> class.
+        /// </summary>
+        public InvalidItemIdException()
+        {
+        }
+
+        /// <summary>
+        /// Initializes a new instance of the <see cref="InvalidItemIdException"/> class with a specified error message.
+        /// </summary>
+        /// <param name="msg">The message that describes the error.</param>
+        public InvalidItemIdException(string msg) : base(msg)
+        {
+        }
+
+        /// <summary>
+        /// Initializes a new instance of the <see cref="InvalidItemIdException"/> class with a specified error message
+        /// </summary>
+        /// <param name="info">SerializationInfo</param>
+        /// <param name="context">StreamingContext</param>
+        protected InvalidItemIdException(SerializationInfo info, StreamingContext context) : base(info, context)
+        {
+        }
+    }
+}
diff --git a/Lib9c/Action/Synthesize.cs b/Lib9c/Action/Synthesize.cs
index 1f5438af8e..417acc506d 100644
--- a/Lib9c/Action/Synthesize.cs
+++ b/Lib9c/Action/Synthesize.cs
@@ -30,6 +30,11 @@ namespace Nekoyume.Action
     [ActionType(TypeIdentifier)]
     public class Synthesize : GameAction
     {
+        /// <summary>
+        /// The list of invalid item ids for material.
+        /// </summary>
+        public static readonly int[] InvalidMaterialItemId = { 10660004, 10760009, 40100042, 40100043, };
+
         private const string TypeIdentifier = "synthesize";
 
         private const string MaterialsKey = "m";
@@ -116,6 +121,15 @@ public override IWorld Execute(IActionContext context)
                 addressesHex
             );
 
+            // Check Invalid Item
+            foreach (var materialItem in materialItems)
+            {
+                if (InvalidMaterialItemId.Contains(materialItem.Id))
+                {
+                    throw new InvalidItemIdException($"{materialItem.Id} is invalid item id.");
+                }
+            }
+
             // Unequip items (if necessary)
             foreach (var materialItem in materialItems)
             {