Later, he went south, where he participates in the last operations of the Siege of the Alcázar, which until then had all been unsuccessful. Once Toledo fell into revolted hands, Burillo was present in different actions of the Front of the center, trying to put order among the militiamen in his column who were demoralized. Later, he participated with his column in the defense of Madrid. At the end of 1936 his column – which would later be militarized and converted into the 45th Mixed Brigade – left the leadership; He went on to lead the newly created 9th Division. With this unit he will be present in some sectors of the Madrid Front, until February 1937, when the start of a Francoist offensive to the south of Madrid occurs. To stop it, the Republicans organized two defense groups: one of them was under the command of Burillo and depended on the Army of the Center under the command of General Sebastián Pozas.