The Colombian's renowned deftness of touch and eye for goal from outside the area saw him fire home just before half-time, prompting a meltdown from the Baggies that saw Kieran Gibbs and manager Slaven Bilic sent off in the immediate aftermath.
It was difficult to understand what prompted the former England left-back to smack Rodriguez in the face as the bump he was given by the ex-Real Madrid playmaker was in no way aggressive.
Bilic has form for emotional outbursts and – even though he must have known he could have little argument with referee Mike Dean – he confronted the official at half-time and was also dismissed. The Croat was probably still seething after seeing the offside flag against Calvert-Lewin's clever back-heeled equaliser correctly overruled by VAR.
West Brom's lack of discipline was staggering considering how much control they had shown over the opening half-hour, in which they had just 36 percent possession – also hitting the post through Jake Livermore – but arguably the better of the game.
It meant Grady Diangana's brilliant first Premier League goal, running from 20 yards inside his own half, was somewhat overshadowed. However, that should not be to the detriment of the 22-year-old, who for 30 minutes outshone the more celebrated and decorated Rodriguez.
Everton manager Carlo Ancelotti stood arms outstretched in his technical area after the £18million summer Baggies signing sprinted through a large hole that should have been protected by one or both of his own summer signings Allan and Abdoulaye Doucoure before whipping a shot past England goalkeeper Jordan Pickford.
A penny for Mark Noble's thoughts after the West Ham captain's very public criticism of the club's decision to sell Diangana earlier this month.
But from there the Rodriguez effect kicked in and, after Calvert-Lewin's equaliser, the hosts moved into the ascendancy. All three of the Everton's striker's goals were real poacher's efforts, stealing his second from Richarlison inches from the goal line and his hat-trick coming via the back of his head. But lying behind it was the class of Rodriguez, who scored his first goal for his new club with two touches and an unerring shot inside the far post to put the hosts ahead.
The Colombian has scored 53 goals in Europe's top five leagues and 34 percent of them have come from outside the area, including three of his last six. And it was in the space between 18-yard line and the centre-circle where the former Real Madrid man was hugely influential.
Matheus Pereira's brilliant free-kick just after the break, leaving Pickford clawing at thin air, had briefly levelled things, but Michael Keane pounced on Richarlison's parried header before Rodriguez threaded a pass through to the Brazilian only for his goal-bound shot to provide the second of Calvert-Lewin's treble.
Rodriguez was withdrawn 12 minutes from time, safe in the knowledge Everton had recorded consecutive victories at the start of the season for the first time since 2012/13, taking the Toffees to the top of the Premier League, if only maybe for a few hours.
But while Ancelotti's new-look side are riding the crest of a wave, there is no easy route off the bottom of the table for Bilic, who watched the second half from Goodison's press box, with Chelsea at home next week.
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