Essex 145 for 5 lead Hampshire 120 (Porter 5-37, Harmer 3-26) by 25 runs
Fast bowler Porter took five for 37 on a bowler-friendly Ageas Bowl pitch, with Simon Harmer assisting with three for 26.
Essex replied by reaching 145 for six before close, to take a 25-run lead into day two, with two wickets apiece for Kyle Abbott and John Turner kept the visitors in check.
Essex won the toss and Tom Westley gleefully put his hosts into bat first on a pitch on which appeared to have been prepared to promote a positive result.
That outcome is needed for both sides, placed second and third coming into this round of fixtures, in their quests to chase down runaway leaders Surrey - who led Essex and Hampshire by 14 and 29 points with four matches to go.
Hampshire are 50 years without a Championship title and is the only trophy Rod Bransgrove hasn't won in his 23 years as chairman - this will be his last chance after announcing his decision to step down at the end of the season before play.
Hampshire openers Ian Holland and Fletcha Middleton were both snared out by Porter before seven overs had been completed.
But Essex's early joy was tainted by Shane Snater - who had replaced the ill Doug Bracewell - limping off after five balls, having pulled out of a delivery just before reaching his stride.
The loss of a main bowler mattered little as Paul Walter stepped up and angled across James Vince, and with Hampshire eventually bowled out inside 39 overs it meant fewer miles in the legs.
Ben Brown was well caught at first slip by Simon Harmer, Nick Gubbins was loose on the drive off Porter and Liam Dawson top-edged a sweep to fine leg to leave Hampshire 79 for six at lunch.
Porter is back to his destructive best this season after a series of lean seasons, by his high standards.
Having put himself on the England radar with Championship wicket tallies of at least 48 between 2015 and 2019, Porter claimed 34 scalps in 2021 and only 19 wickets last season, with Sam Cook rising to lead the attack.
His five at the Ageas Bowl took him to 42 wickets for the season - only spinning team-mate Harmer and Nottinghamshire's Brett Hutton have more.
Porter was rewarded for his potent accuracy with his second five-for of the season by spearing into Felix Organ's back pad, before James Fuller advanced and slapped the next ball he bowled to deep cover.
Harmer wrapped up the tail with Turner edging to slip and Mohammad Abbas slogged to long on as Hampshire were bowled out for 120.
In reply, Nick Browne was bowled by Abbas in the fifth over. as the pitch remained unmoved in its bowling friendliness.
Abbott picked up Alastair Cook and Paul Walter in a double wicket maiden to see Essex to 16 for three and in danger of copying Hampshire's low score.
But Essex did something Hampshire couldn't do; form partnerships.
Only Gubbins and Vince's 39-run stand had topped 20, while Tom Westley and Matt Critchley added 41 before Critchley and Michael Pepper scored 36 together before Pepper and Adam Rossington joined forces for 25.
Vince, who managed to negotiate his way to three replacement balls, only called on Vitality Blast hero Turner in the 34th over.
The wait had Turner raring to go as he bounded in to crash into Critchley's pads first ball before later finding Pepper's outside edge.
Essex edged into a first-innings lead with Rossington and Harmer reaching the end of the day with a platform to secure an important first-innings lead.