Vladimir Kravinov was first shown in Spider-Man #47-48 (at least to my knowledge). In this issue, Jason Macendale, aka Hobgoblin, was searching for a way to increase his power. He was tired of being humiliated by Spider-Man. He journeyed to the Kravinov estate located somewhere in the Ural Mountains in Russia. Macendale wanted Kravinov to give him the serum that gave Kraven his strength. In return, Macendale was willing to give Vladimir one of his father's missing journals. Vladimir wanted to kill the Hobgoblin immediately. However, his family's trusted advisor, Gregor, convinced him to give Macendale the serum. Vladimir had been trying to improve on his father's formula to make his strength permanent. Kraven had to continually recharge his powers. Gregor hoped to experiment on Macendale so nothing would happen to Vladimir. They planned to kill Macendale if the experiment was a success. However, Jason had a backup plan. He had hid his goblin glider, which was loaded with pumpkin bombs, near the estate. After he was administered the serum, he gained immense power. Before, Gregor could kill him, Macendale signaled for his glider and weapons. It was learned that Macendale had an anomaly in his blood stream that interacted with Kraven's serum. He was able to keep the powers of Kraven without dying from the formula as Gregor had hoped. Macendale escaped with his newfound power.
Vladimir did receive his father's journal from Macendale and became obsessed with avenging his father's death. He blamed Spider-Man for his father's suicide. He took his father's serum and gained all of the powers of his father. As he became more obsessed, Gregor became more worried. He worried that the same thing that happened to Kraven would happen to Vladimir. Vladimir first fought Spider-Man in Spider-Man #50. At the time Peter was still trying to deal with the death of his "parents" and the aftermath of the Pursuit storyline. He was trying to overcome his "I am the Spider" thing. The Grim Hunter drugged Spidey and almost had the advantage. In a wonderful panel, Spider-Man was knocked into the river. He thinks that he is not just the Spider and as he arose from the river, he shouts he is Spider-Man. He quickly defeats Vladimir and then Gregor arrives in a helicopter. He threatened to shoot Spider-Man. However, Spidey rips him out of the helicopter and then destroys it. Gregor told Spider-Man that the Grim Hunter would not rest until he was dead.
In the Web of Life story arc [Web of Spider-Man #120,121 and Spider-Man #54-55] the Grim Hunter battles the Scarlet Spider. In Web #120 he picked up what he thought was Spider-Man's scent. In reality it was Ben's who was visiting Betty Brant in costume. The Scarlet Spider was interested in Betty but she said she was remaining objective in her story about him. After Ben left, the Grim Hunter arrived and demaned to know where the Spider was. Betty did not realize that Vladimir thought Ben was Spider-Man. She told him that he just left. In Spider-Man #54, Ben returned to Betty's apartment. However, the Grim Hunter followed him there. They clashed and Vladmimir makes a comment about Ben trying to change his costume to avoid the Grim Hunter. As you can guess, Ben was very confused. During their battle, Vladimir noticed that Ben's fighting style was slightly different from Spider-Man. He then left Ben in search of the real Spider-Man.
Ben set out to stop the Grim Hunter before he could track Spider-Man back to his home. Kaine in the meantime had another vision of Mary-Jane's death. Ben traveled to Peter and Mary-Jane's apartment and Kaine followed him there. He started to fight Ben and hit the Scarlet Spider with a large rock. The Grim Hunter had witnessed this and confronted Kaine. He warned Kaine that he had better not interfere with his conflict with Spider-Man. Kaine was not big on being threatened so he attacked Vladimir. Their conlict ended in Spider-Man #55. In a Ben tried to stop them, but he was unsuccessful. Gregor followed Kaine and the Grim Hunter as well. During the course of their battle, Kaine gained the upperhand and The Grim Hunter died from the "Mark of Kaine". Gregor grieved over his dead body. Gregor's fear came true. Kraven's legacy was passed on to his son. The Hunt ended in Vladimir's death.
