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Saikat GangulySaikat Ganguly 

Call external WS on click of Standard button like 'save' or other.

Is there a way to call external WS on click of a Standard buttons using Apex.? Or is it possible to call external WS on click of Standard buttons?.

The thing I want to do is, When admin of a salesforce account added a new value in a picklist so on 'save' button of a new picklist value I want to call an External WS for some further updation at my end.?

Is there is  a way to do.. I already got an idea about external WS call on Cutom buttons but I want to do the same thing on Standard Buttons
Thanks in advance.
No, there is no way to do this with standard buttons.  You can override the functionality by creating a custom Visualforce page with a standardcontroller and a custom extension [1].  Then as part of the save method, do your callout.

Alternately if you do not need the call to occur synchronously, you can do the callout as part of a trigger and have it fire asychronously.