Two shots were fired towards City of Wolverhampton College during class just after 2.30pm on Monday.
Nobody was injured as the bullets hit a wall at the college on Paget Road, which is opposite St Judes C Of E Primary School.
Students and staff were moved to a place of safety by staff and police were called but lessons otherwise continued as normal.
The college is open as usual today.
Officers have been searching the area and studying CCTV but it is not known where the shots came from and nobody has been arrested over the incident.
Chief Inspector Hasson Shigdar, from Wolverhampton Policing Unit, said: “We are deeply concerned that a firearm has been discharged in broad daylight in the vicinity of the college and also a primary school.
"We are doing all that we can to trace those responsible and I would ask anyone with information to contact us urgently.
“We do not believe that anyone in the college was targeted as the view into the building is restricted, however we have increased our patrols to offer reassurance to students and residents in the area.
“We have liaised with the college who are also supporting their students and staff."
Malcolm Cowgill, principal of the college, said: “I can confirm that an incident occurred on Paget Road on the afternoon of Monday, 28 September.
“No students, apprentices or staff were harmed and our security staff immediately attended the scene to evacuate the area.
“We take the safety of our students, apprentices and staff extremely seriously and have assisted police with their inquiries, however as this is an ongoing investigation it would not be appropriate for us to comment further until this has been concluded.
“This was an isolated incident and lessons continued in other buildings on the campus throughout the rest of the day.
“Students, apprentices or parents who may have been affected by the incident can contact the college’s counselling team on 01902 317689 (Monday-Thursday 9am-5pm and Friday 9am-4.30pm) or by email: email@example.com.
" Out of hours support is also available at www.wolvcoll.ac.uk/mental-health
“The Paget Road campus is open as usual today and classes are continuing as planned.”
Police can be contacted via Live Chat on the website at west-midlands.police.uk between 8am and midnight, or by phone on 101 anytime quoting log 2630 of 28/9. Information can be given anonymously to Crimestoppers on 0800 555 111.