with不可以引導定語從句，例如：

1.She is a doctor with a strong sense of vocation.她是一位具有強烈使命感的醫生。

2.She moves with the natural grace of a ballerina.她的動作具有芭蕾舞演員自然優雅的丰姿。

3.The school has established a successful relationship with the local community.這所學校與當地社區建立了良好的關系。

例句：

.The pen with which he is writing is mine.

with which是“介詞+關系代詞”結構，常用來引導定語從句.

with有“用 “的意思，介詞之後只能用which，不能用that. with which在定語從句中作狀語，即he is writing with a pen.

定語從句

The person over there is the one (who taught me English).（引導詞：who）

The pretty lady (whom you met yesterday) is a famous actress.（引導詞：whom）

2.狀語從句When he arrived at the airport, the plane had taken off.（引導詞：when）I didn't go to school yesterday because I was ill.（引導詞：because）

3.with結構：

He stood in the wind with his nose red.He slept in the room with the light on.

She came in with nothing in hand. He came out of the workroom with the machine running.

The soldier was brought in with his hands tied back.

I can't go to see the film with so much work to do

with只有介詞詞性，不能引導定語從句，詳解如下。

定語從句（也稱關系從句、形容詞性從句），一個簡單句跟在一名詞或代詞後（先行詞）進行脩飾限定，就叫做定語從句。

這個簡單句在主句中充當定語成分，被脩飾的詞叫先行詞。定語從句不同於單詞作定語的情況，它通常只能放在被脩飾的詞（即先行詞）之後。定語從句由關係詞（關系代詞、關系副詞）引導，關系代詞、關系副詞位於定語從句句首。