A320
Flight Crew Air Transport Pilot (ATP); Flight Crew Multiengine; Flight Crew Instrument
Flight Crew Last 90 Days 200; Flight Crew Total 20500; Flight Crew Type 7500
Communication Breakdown
Aircraft Equipment Problem Less Severe; Deviation / Discrepancy - Procedural Published Material / Policy; Flight Deck / Cabin / Aircraft Event Smoke / Fire / Fumes / Odor
Flight Crew Took Evasive Action; General Flight Cancelled / Delayed; General Maintenance Action
Human Factors
I boarded the aircraft. Temps were below freezing at night so I looked out of the jetway on the way in to the airplane to verify if the wing looked like it had frost and if external air was hooked up.  I couldn't see if the wing was clear and saw no de-ice fluid dripping or de-icing in progress also there was no external air connected to the aircraft (air at gate X has been broken for weeks if not months). The flight attendants were already onboard and it was cold when I boarded. Since boarding was in 15 minutes I elected to start the APU just before briefing the flight attendants.  I turned on the APU bleed and proceeded to brief then about 3 minutes into the brief; smoke started pouring out of the air conditioning system throughout the aircraft. I immediately ran forward and shutoff the bleeds and APU. I then ran to the gate (faster than trying to get iPad out in smoke for OPS freq.) and told agent to ask for fire response due to smoke.  I immediately went back [to] the aircraft and verified the flight attendants were off of the plane and continued outside to make sure the aft cargo compartment door wasn't opened until the fire trucks arrived since we had warnings for that compartment. I elected not to fire the bottles since I could smell the de-ice fluid.  As I exited the jetway I saw ground services spraying the airplane next door after having just doused my airplane (there was an unbelievable amount of fluid coming off of my plane). The fire trucks arrived after a few minutes and I explained what I believe to be going on and they verified it with an inspection of the aircraft.  The smell inside the airplane was intense so I made sure that we would not be boarding. I then called Maintenance Control; the Chief Pilot; my Dispatcher and ZZZ Station OPS to advise everyone of the situation.  After everything was verified under control; I went out to the gate and made a PA announcement to the passengers about why there were fire trucks around our airplane. I then went back and coordinated with Maintenance Control and scheduling.
A320 Captain reported a fume event during preflight at gate due to a communication breakdown between flight crew and deicing ground personnel.