Police said the crash happened at 07:10 on the B7066 Whitburn Link Road, near Polkemmet Country Park.
Several roads have been closed. They are due to open at 12:30.
The 58-year-old man who died was a driver in the stationary car.
The occupants of the van suffered minor injuries. Police are appealing for witnesses.

The Teaching Excellence Framework (TEF) has rated 295 institutions bronze, silver or gold according to their standard of undergraduate teaching.
Bangor University was awarded gold, while five other colleges got silver. One - University of Wales, Trinity St David - got bronze.
Aberystwyth University and University of South Wales opted not to take part.
Across the UK, 59 institutions got gold, 116 silver and 56 bronze.
Others received a "provisional" ranking, where there was not enough data for a full assessment.
Bangor's vice chancellor John G Hughes said the ranking "reflects its impressive performance".
The TEF is administered by the Higher Education Funding Council for England and degree providers could choose whether or not to take part.
They were assessed on a range of measures, including teaching quality, student satisfaction, drop-out rates and whether students go on to employment or further study after graduating.
A gold award means a university is of the highest quality found in the UK, providing "consistently outstanding teaching, learning and outcomes for its students", while the silver award was given for consistently exceeding "rigorous national quality requirements for UK higher education" and bronze was awarded to those that met these national requirements.
Those awarded a bronze or higher are now set to be able to raise tuition fees, which currently stand at around Â£9,000.
"Bangor has maintained a strong commitment to the delivery of high quality student experience for many decades," Prof Hughes added.
"Not only do we link research and teaching, but we also provide personalised pastoral care, and provide variety and experimentation in our teaching and learning.
"We strongly believe that students deserve to be exposed to, and to be stretched by, the rigour and intellectual challenges of problem solving within their disciplines."
Dr Mirjam Plantinga, Pro Vice-Chancellor for Student Experience at University of Wales Trinity St David, said: "We are pleased that the panel has recognised good levels of student satisfaction with academic support, and assessment and feedback.
"Together with a focus on employer engagement and our distinctive culture, our TEF result reflects positively on the key values that underpin the UWTSD student experience".

12 September 2014 Last updated at 06:51 BST
But the contrast could not be more different in India where consumers are being bombarded with low-priced smart devices.
These cheaper handsets are set to open up new online opportunities, as millions of people take to the internet for the first time.  From Delhi, David Reid reports.
Watch more reports on Asia Business Report's website.
A man has died after a van crashed into a stationary car in West Lothian.
[NEXT_CONCEPT]
Only one Welsh university got the highest possible score in a new ranking of degree teaching standards.
[NEXT_CONCEPT]
Smartphones were one of the big themes of the week  - and the release of Apple's latest iPhone could well shake things up at the top end of the market.