with不可以引导定语从句，例如：
1、She is a doctor with a strong sense of vocation.她是一位具有强烈使命感的医生。
2、She moves with the natural grace of a ballerina.她的动作具有芭蕾舞演员自然优雅的丰姿。
3、The school has established a successful relationship with the local community.这所学校与当地社区建立了良好的关系。
例句：
The pen with which he is writing is mine.
with which是“介词+关系代词”结构，常用来引导定语从句.
with有“用 “的意思，介词之后只能用which，不能用that. with which在定语从句中作状语，即he is writing with a pen.
定语从句
The person over there is the one (who taught me English).（引导词：who）
The pretty lady (whom you met yesterday) is a famous actress.（引导词：whom）
2、状语从句When he arrived at the airport， the plane had taken off.（引导词：when）I didn't go to school yesterday because I was ill.（引导词：because）
3、with结构：
He stood in the wind with his nose 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只有介词词性，不能引导定语从句，详解如下。
定语从句（也称关系从句、形容词性从句），一个简单句跟在一名词或代词后（先行词）进行修饰限定，就叫做定语从句。
这个简单句在主句中充当定语成分，被修饰的词叫先行词。定语从句不同于单词作定语的情况，它通常只能放在被修饰的词（即先行词）之后。定语从句由关系词（关系代词、关系副词）引导，关系代词、关系副词位于定语从句句首。
