Danielle Brooks
一位樸實，有錢的典型喬治城媽媽，Danielle是Annie可靠的姐姐。擁有兩個小女兒和身任高職的老公，她走了一條有別於Annie的人生道路，過著穩定安逸的生活。有時候她日子過得充實，而有時候她就像一本道德啟示故事集，想要提醒Annie。她總是認為Annie太賣命工作，她應該要忘記舊愛並且再次約會談戀愛。在知道她心裡還牽掛著舊愛時，她並不知道Annie是中情局情報員，這也正是為什麼Annie可以成為理想的情報員的原因。然而在本季中Annie將會和姊姊透露自己是情報員的秘密…。
A grounded, somewhat earthy yet affluent Georgetown mom, Danielle Brooks (Anne Dudek) is Annie's reliable older sister. While juggling two young daughters and a husband with a high-powered job, Danielle represents the path not taken for Annie, one that's rooted and safe. At times Danielle represents the life fulfilled and at other times she's the cautionary tale. Danielle thinks Annie works too hard and that she needs to move on and start dating again. Danielle is unaware her sister is working at the CIA and while she thinks her sister is emotionally unavailable, it's this exact quality what makes Annie an ideal CIA operative.
Joan Campbell
比起其他身處在男性主導的中情局裡，Joan試圖努力往上爬，獲得升遷。為此她努力堅持，下定決心和保持冷靜。她對她的新員工Annie很嚴格，因為在她身上看到過往的自己，儘管她不承認這點。而Annie也不了解Joan對她冷酷嚴格是因為要保障她的安全，並且能使她成長，成為一名更優秀的情報員。因為嫁給她的老闆Arthur，她身處一個尷尬位置。維持家庭和工作間的界線對這對夫婦來說永遠是個挑戰，尤其是Joan懷疑丈夫背著她外遇偷吃。
Joan (Kari Matchett) has managed to ascend higher in the CIA than almost any other woman in a male-dominated agency. She's done it with grit, determination and poise. Joan is hard on Annie, her newest employee, because she sees herself in her. Not that she would ever admit it. And Annie doesn't realize that Joan's ferocity comes from a need to protect her, and make her a better agent, not compete with her. Joan is also in the difficult position of being married to her boss, Arthur. Maintaining the boundaries between home and work is a constant challenge for this couple, particularly since Joan suspects that her husband is cheating on her.
Arthur Campbell
Arthur是中央情報局的國家情報部部長。氣宇非凡，一言九鼎，他生性愛鬥，不管是跟美國的敵人或是和他一樣在情報局工作的妻子Joan鬥嘴吵架。然而他希望能讓中情局作業有多一點透明度的想法和單位的天性相齟齬。他有他的支持者，雖然大家可能不承認，但並非人人都認同他的想法。他身陷在中情局鬥爭當中，而一定會有人受到波及被犧牲。
Arthur (Peter Gallagher) is the director of the Clandestine Service Department at the CIA. A regal and imposing presence, he loves a good fight whether it's with a known enemy of the United States or verbal sparring with his own wife, Joan, who also works at the Agency. But his bid to bring more transparency to the CIA is at odds with the very covert nature of the organization. Arthur has his supporters but not everyone's on his side, whether they'll admit to it or not. He's in for an uphill battle that's sure to have its casualties.
Jai Wilcox
第二代接棒的中情局幹員，Jai (Sendhil Ramamurthy飾)，之前是耶魯的運動風雲人物。Jai不認輸的態度事實上非常適合金融業，但他選擇當個探員。生性風流倜儻，處處留情，包括國會助 理，中情局同事和去參加好友在冰島雷克雅維克舉辦的單身派對，飛行途中遇到的空姐都是他的約會對象。
A second-generation CIA man, Jai (Sendhil Ramamurthy) was a former lacrosse star at Yale. Jai's hate-to-lose attitude would make him a perfect fit for investment banking, but he's chosen the Agency route instead. He has dated everyone from Congressional staffers to other CIA workers to a flight attendant he met while flying to a buddy's bachelor party in Reykjavik.
Auggies Anderson
前任中情局探員Auggie(Christopher Gorham)在一次任務中因意外失明。現在任職於國家防衛部門的科技部門擔任內勤人員。Auggie了解鮮為人知的中情局組織內的複雜內情。Annie 一來，Auggie很快就知道她的聰明伶俐，結為好友，並且盡其所能幫她。他深深了解Annie，因此願意相信她的直覺。在本季中他和Annie的夥伴關係是否會生變，產生不同的化學變化？
A former CIA special operative, Auggie (Christopher Gorham) was blinded during a mission. He is now heading up the tech ops department within the DPD. Auggie understands the intricacies of the massive bureaucracy of the CIA in a way that few others do. He immediately picks up on Annie's intelligence and takes her under his wing to help her navigate the system. He sees Annie for who she really is and because of that, is willing to follow her instincts.
Annie Walker
或許對政府最機密的機關單位來說還是菜鳥，但28歲的Annie有著異於常人的本能直覺、韌性和毅力，這些特質讓這位鄰家女生變成致命武器。雖然她首次任務結束在槍林彈雨之中，當她被中情局升遷到實演場時但她不慌亂也不猜想她的未來的走向。她心中只想要做好工作，完成任務。第二季中將會繼續到各國出任務，而她的私生活和感情會有更多變化。
She may be new to the government's most secretive branch, but 28-year-old Annie Walker (Piper Perabo) has the uncanny instincts, tenacity and persistence that could make this girl-next-door a lethal weapon. Although her first mission unexpectedly ends in a hail of bullets, Annie doesn't get flustered or second-guess her new career path when the Agency unexpectedly promotes her to field operative. If anything, it has made her more determined to be good at her job and see her assignments through.