Big Shots received favorable reviews from critics. Sam Samuelson of AllMusic gave the album 3 stars out of 5, calling it "a treasure that should be cherished by hip-hop fans the world over." Nathan Rabin of The A.V. Club commented that "[Peanut Butter Wolf's] gorgeously constructed tracks, flawless ear for melody, and extensive sonic quotations anticipate Madlib." Rachel Swan of East Bay Express felt that "[Charizma] might've turned into another Pharoahe Monch or J-Live." Todd Inoue of Metro Silicon Valley noted that "Charizma sounds like MC Shan blessed with youthful lung capacity while PB Wolf makes like Marley Marl programming beats in DJ Premier's lab." Ross Hogg of XLR8R wrote, "Charizma's voice brims with eagerness, enthusiasm and earnestness; Wolf's textured, jazzy beats epitomize boom bap and are a sign of great things to come."