This is first time I have to apply for Non-Immigrant B for me and Non-Immigrant O for my wife (same nationality).

When I come to Thailand then my employer will get Work Permit for me.

My Question is: Is it possible to apply my wife's visa along with me while having no work permit (at first time).

Thank You.

Believe most Consulates can issue as below requirement:

A letter from your spouse or family member's visa sponsor in Thailand verifying current status of relationship

A copy of your spouse or family member's passport personal detail page and Thai visa

Believe most Consulates can issue as below requirement:

A letter from your spouse or family member's visa sponsor in Thailand verifying current status of relationship

A copy of your spouse or family member's passport personal detail page and Thai visa

How can my employer verify current status of relationship ? Do they need to verify using 3rd party.

Any related information is really appreciated.

Thank you.

You provide proof of marriage and your passport data page and visa. There is an option to have a visa sponsor provide such information (such as Thai wife).