Although theoretically possible, travelling from Bangkok to Phnom Penh is a single day is not particularly practical. Instead break the journey over night at either Battambang or Trat/Koh Kong (or even Koh Chang) dependent on the route you select. There are two possible routes between the two cities, the most common one being the Poipet border crossing also used when heading to Siem Reap. The other crosses the border at the more southerly crossing at Hat Lek.
Via Poipet:
There are 2 trains daily from Bangkok Hualamphong station bound for Aranyaprathet, journey times are around 5.5 hours and the train departs at 0555 and 1305, in order to be able to cross the border on the same day you will need to take the 0555 departure. Alternatively there are regular buses from Mo Chit bus terminal for Aranyaprathet taking around 4.5 hours. Train fares are 50 baht compared to bus fares of around 150 – 200 baht depending on class of bus.
From Aranyaprathet you will need to take a tuk-tuk or a motorbike taxi to the Cambodian border town of Poipet, this can reasonably cost somewhere between 50 – 80 baht. The border is open from 0700 to 2000 and you can get your Cambodian visa on arrival for $20. There are no regulations to say you must change money at the border, do not listen to anyone who claims this is the case.
From the border you will see signs advertising free transport to the bus station from where you can organise a shared taxi to Battambang (around 2 hours). You may need to change cars Sisophon. Spend the night in Battambang before taking a direct bus on day 2 to Phnom Penh. The onward journey to Phnom Penh will take around 5.5 hours and fares are around $4.
Via Hat Lek:
There are regular buses from Bangkok's Ekkamai bus station to Trat (which is also the starting point for a trip to Koh Chang.) In Trat you are around an hour from the border, so dependent on time of day you may which to spend the night before heading on to Phnom Penh the following day. You may also want to seriously consider breaking the journey for a few days on Koh Chang if you are not in a hurry.
From Trat take a van to the border at Hat Lek, the vans depart from the same place as the Bangkok bus arrives and run to a published schedule. There is also a set fare of 100 baht. From where you are dropped by the van you can walk through the Cambodian border controls where your visa on arrival is supposed to cost $20. In reality at this border post you are unlikely to pay this as officials will demand a larger sum.
Once through the border take one of the motorbike taxis into Koh Kong, don't pay any more than 50 baht and insist the driver uses the bridge rather than dropping you at the water taxis. From Koh Kong you can organise a seat in a share taxi for around $10 - $20 ($20 for the whole front seat) or you can get the whole car for around $60. The journey from Koh Kong to Phno Penh takes between 6 – 8 hours dependent on delays.
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