Murilo Santana began his Brazilian Jiu-Jitsu journey under the mentorship of Mario Yamasaki and the Yamasaki brothers in Brazil. Demonstrating exceptional dedication and technical aptitude, Santana earned his black belt directly from Mario Yamasaki. Following Yamasaki's relocation to the United States, Santana transitioned to training under renowned coach Marcos Barbosa, representing Barbosa's academy in São Paulo, Brazil.

Technical Mastery and Competitive Highlights

Throughout his competitive career, Murilo Santana established himself as a technical powerhouse, particularly renowned for his relentless guard passing and suffocating pressure game. His notable achievements include winning the ADCC Brazilian Trials and competing four times at the prestigious ADCC World Championship, where he notably secured a 4th-place finish at the 2011 ADCC World Championship.

Santana's technical prowess earned high praise from multiple-time world champion Bernardo Faria, who described him as one of his toughest training partners. Even after shifting his primary focus to coaching, Santana continued to compete selectively, capturing gold at the 2023 IBJJF Nashville Open.

In 2015, Murilo Santana relocated to New York City to co-found Unity Jiu-Jitsu, quickly establishing it as a premier competition-focused academy. Unity gained recognition for its intense training environment, where world champions and dedicated lower belts trained side-by-side. Santana implemented an open-door policy, welcoming elite athletes from various teams to foster an "iron sharpens iron" atmosphere. Under his leadership, Unity expanded internationally, conducting training camps in Puerto Rico and Europe, with plans for additional affiliated academies worldwide.

Santana's coaching philosophy emphasizes rigorous training, technical precision, and open collaboration among athletes. Under his guidance, numerous competitors rose to prominence, including multiple-time world champion Mayssa Bastos and elite black belt Devhonte Johnson. Additionally, Santana provided a training home for renowned athletes such as the Miyao Brothers. His approach consistently produced results, with Unity athletes regularly capturing gold at major tournaments, including ADCC Trials and IBJJF No-Gi Worlds.

In September 2022, Murilo Santana was involved in a high-profile altercation at the ADCC Open in Las Vegas, Nevada. During a scuffle involving his student Jeferson Guaresi and an opposing entourage, Santana was captured on video brandishing an object described by officials as a knife. This incident resulted in a lifetime ban from ADCC events, issued by ADCC organizer Mo Jassim. Santana publicly apologized for his actions, clarifying he never intended harm and accepted the consequences. Despite the incident, Santana maintained a largely positive standing within the broader Brazilian Jiu-Jitsu community, continuing his influential coaching and mentorship roles.

Widely respected for his world-class guard passing and relentless pressure techniques, Murilo Santana is frequently cited by peers and students for his exceptional technical depth. His skills, often described as elite even during training sessions, have sparked considerable discussion among grapplers regarding his potential had he competed more frequently. Santana himself, however, has expressed contentment in prioritizing coaching and student development over personal competitive accolades.

As of 2025, Murilo Santana remains actively involved in expanding Unity Jiu-Jitsu's global presence, with plans to establish new affiliated academies in various cities. While a return to the world championship stage as a competitor appears unlikely, Santana has expressed openness to occasionally competing in Masters-level events purely for enjoyment. His ongoing commitment to coaching and mentorship continues to significantly impact the Brazilian Jiu-Jitsu community.