Two ambulances, two paramedic officers and others were called to Tipton Road, in Woodsetton, at 8.35pm on Thursday.
The crews discovered a man in a critical condition who was already receiving medical assistance from a bystander.
Crews provided advanced life support but nothing could be done to save him and he died at the scene, the service said.
A spokeswoman for West Midlands Ambulance Service said: “When ambulance staff arrived, they found two patients, a man and a woman, had been involved in a collision with a car.
“The man was found to be in a critical condition and was already receiving medical assistance from a bystander.
“Ambulance crews worked quickly to provide advanced life support but sadly, despite everyone’s best efforts, it became clear that nothing more could be done to save him, and he was confirmed dead at the scene.
“The woman was treated for serious injuries by ambulance staff before being conveyed on blue lights to Queen Elizabeth Hospital in Birmingham for further treatment.”
Two ambulances, two paramedic officers, the Critical Care Car from The Air Ambulance Service in Strensham, a MERIT trauma doctor and critical care paramedic were sent to the scene.
Resident Doreen Davis said she witnessed flashing lights and people wearing high-vis jackets in the area. She said: "It must have been horrible."
Another resident Janet added: "There was a lot of police activity in the area and I saw them putting police tape up around the streets."
Lisa Cookley said: "It's really horrible, my thoughts are really with their families."