Munro fell for 56 and Guptill was gone for 31, while Rumman Raees lbw'ed Ross Taylor for 1, reducing New Zealand to 90-3.
Shadab struck again to send Tom Latham back to the pavilion, with New Zealand 99-4.
Skipper Sarfraz Ahmed and veteran batsman Mohammad Hafeez earlier steered Pakistan to a respectable total of 262.
Fakhar Zaman and Haris Sohail - in for out-of-form Azhar Ali - both scored sure-footed fifties after Pakistan won the toss and chose to bat.
Fakhar scored 54 off 75 balls before falling to the spin of Mitchell Santner. Faheem Ashraf, opening the innings after Imam-ul-Haq was ruled out of the match due to injury, could not fire and went for 1 off a Tim Southee delivery.
Haris Sohail stabilised Pakistan's innings with a steady 50 off 74 balls before getting out off Kane Williamson's bowling.
Just as Pakistan seemed to slow down, Mohammad Hafeez and Sarfraz Ahmed hit fifties in the later overs to keep the momentum going.
Hafeez scored 81 off 80 before getting run out, while Sarfraz put up 51 off 46 before falling to Trent Boult.
Paceman Tim Southee led the New Zealand attack with three for 44 and skipper Kane Williamson took two for 32.
Earlier, during toss, Sarfraz praised the pitch. "It looks like a good pitch, so hopefully we can make a good score," he said.
New Zealand skipper Kane Williamson was unperturbed about losing the toss, saying conditions early in the match should suit his pace attack.
"We were actually going to have a bowl," he said. "In some of these day-night games perhaps you´ll get a bit of dew later on."
New Zealand have already won the five-match series after taking a 3-0 lead in Dunedin on Saturday and are chasing a record 11th consecutive win in all formats of the game.
Shoaib Malik head blow
All-rounder Shoaib Malik was hit on the head by a wayward throw during batting. He got up and continued to bat, but has now been rested due to some signs of delayed concussion.
"While trying to take a run Shoaib Malik was hit on his head with a wayward throw. Shoaib was assessed on field by match doctor and myself," said Pakistan Team Physiotherapist Vib Singh after the innings.
"He did not have any symptoms of a concussion and was able to carry on playing. After getting out he was reassessed and was showing delayed concussion signs. He is doing well and is resting. As advised by match doctor and team physio, he will not be taking any further part in this match."
Playing XI
Pakistan:
Faheem Ashraf, Fakhar Zaman, Babar Azam, Haris Sohail, Mohammad Hafeez, Shoaib Malik, Sarfraz Ahmed (capt), Shadab Khan, Mohammad Amir, Hasan Ali, Rumman Raees.
New Zealand:
Martin Guptill, Colin Munro, Kane Williamson (capt), Ross Taylor, Tom Latham, Henry Nicholls, Colin de Grandhomme, Mitchell Santner, Tim Southee, Lockie Ferguson, Trent Boult.
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