A solitary first half effort from French striker Fredi Kanoute was enough to secure the win in a competitive and lively encounter at Southend United's Roots Hall stadium, just 10 days before Glenn Roeder's men kick-off the new Premiership campaign at Newcastle United.
Kanoute's fellow countryman, recently signed midfielder Edouard Cisse, made his debut in Hammers colours, while goalkeeper David James captained the side in the absence of injured duo Paolo Di Canio and Steve Lomas.
Hammers made a bright start after kick-off had been delayed for 20 minutes due to Vitesse's coach being held up in traffic on their way to the stadium, and Jermain Defoe came close to open the scoring as early as the second minute, when Kanoute escaped down the right and cut back a low cross that the youngster sliced narrowly wide.
Joe Cole then began to stamp his authority on the game and, after winning two free-kicks in dangerous positions following mazy runs at the heart of the Vitesse defence that were halted unfairly, the young England midfielder went close in the eighth minute with a curling left-foot shot that goalkeeper Jevric did well to keep out.
The Hammers finally got the breakthrough they deserved in the 27th minute, and unsurprisingly it was Cole who provided the moment of magic to separate the two sides. Turning neatly on the edge of the area, he switched a clever reverse pass into the path of Kanoute, who beat the offside trap and stabbed the ball home from six yards out.
Five minutes later, Trevor Sinclair almost doubled the lead with a fierce low shot that Jevric turned around his near post, while Defoe went close on the stroke of half-time with a stinging left-foot effort that whistled just past the post.
Debutant Cisse was replaced at half-time by Richard Garcia, who almost made an instant impact when he raced on to Cole's threaded pass seconds after the restart but the young Australian midfielder showed too much of the ball to Jevric and could only toe-poke his shot wide.
Having been largely a spectator for the majority of the first half, Hammers keeper David James was then called into action, superbly tipping round a curling free-kick from Theo Janssen.
Defoe went close again in the 52nd minute, shooting just over after Cole and Kanoute had combined well on the right, before the 5,773 crowd shrugged a collective sigh of disappointment at seeing Cole's contribution to the evening brought to a premature end as substitute John Moncur took his place in the 71st minute.
A speculative overhead scissors kick from Defoe flew just wide in the 81st minute as the young striker battled in vain to preserve his record of scoring in every pre-season friendly so far this summer.
With seven minutes remaining, Defoe was replaced by 18-year-old French striker Youssef Sofiane, who looked lively up front, but it was the visitors who came closest to snatching an equaliser in the dying moments, as a dangerous corner from the right whizzed across the six yard box before being cleared to safety.
Hammers then held on to secure the win and also capture the reward for their efforts - the Out Performance Display Cup, kindly provided by the match sponsors.
West Ham (4-4-2): James; Schemmel (Breen 65), Pearce (Johnson 79), Dailly, Winterburn (McCann 84); Cole (Moncur 71), Cisse (Garcia 45), Carrick, Sinclair; Defoe (Sofiane 83), Kanoute (Camara 77). Subs unused: Van der Gouw, Courtois, Forde.
Vitesse Arnhem: Jevric, Cornelisse, Stefanovic, Knol (Zeman 69), Mbamba, Janssen, Martel (Riga 57), Levchenko, Peeters, Nanu, Sone. Subs unused: Frankel, Van Beukering, Van Fessem, Hofs, Amoah.