Development of the S-25 was authorized on 9 August 1950 by a decision of USSR and was appended by Stalin: (We have to get the missile for air defense in a year). The system was assigned to design to SB-1 (Special Bureau No. 1).

The initial design included:

• E\F band A-100 "Kama" radar based in two concentric rings; a near ring - 25–30 km from Moscow, and a far ring, approximately 200–250 km from Moscow, for early warning and target detection.
  
• B-200 missile targeting radars, deployed in two rings.
  
• V-300 SAMs deployed around the B-200 radars.
  
• G-400 Interceptor aircraft. These were Tu-4 with G-300 (izdelie 210, downsized version of V-300 with aerial launch) missiles.
  
• Possibly, Tu-4 based AWACS aircraft D-500.
  

The first combat elements of S-25 were delivered to the military in 1954. In March 1954 most sites were being prepared for the installation of the missiles and launchers. The final tests were completed in the beginning of 1955. The first batteries entered service on 7 May 1955. The system entered combat duty in June 1956. The launchers were located at a distance of 75–85 km from Moscow, a dense ring (at a distance of 10–15 km from each other). The locations were masked by forests.

After the system have entered service some parts of Glavspetsmash (Glavspetsmontazh and Glavspetsmash) were disbanded, the KB-1 was transferred to the Ministry of Defense Industries.

In order to operate the S-25 system, the "Separate Army for Special Purposes" was established under the command of general-colonel K. Kazakov in the spring of 1955, being part of Soviet Air Defense Forces (PVO Strany).

A number of improvements was made to the initial S-25 design during the service. The latest modernized S-25M was retired and replaced with S-300P air defense complexes in 1982. Most sites of the original S-25 complex were dismantled in the 1990s and are now summer cottage developments for Moscow residents.